JP2002116521A - Heat developable photosensitive material and image forming method using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a simply and rapidly processable silver halide color photographic sensitive material forming a color image of high image quality excellent particularly in color saturation. SOLUTION: When at least (a) photosensitive silver halide, (b) a reducible silver salt, (c) a color developing agent of formula (I), (d) a coupler which reacts with the color developing agent and forms a dye, (e) at least, one compound of formula (SC-1) or (SC-2) and (f) a binder are held on the same face of the base of a heat developable photosensitive material, a color image having little color mixture and high color saturation can be formed in a heat developing system without increasing fog or deteriorating raw stock preservability.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a photothermographic material suitable for simple and rapid processing, and more particularly to a simple and rapid processing type silver halide color photographic light-sensitive material capable of forming a color image having high image quality, especially excellent color saturation.

[0002]

2. Description of the Related Art A method of forming an image by thermal development is described in, for example, U.S. Pat. Nos. 3,152,904 and 3,457,075, and
Klosterboer, "Thermally Processed Silver System"
s) "(Imaging Processes and Materials) Neblett
e Eighth Edition, J. Sturge, V. Walworth, A. Edited by Shepp, Chapter 9,
279, 1989). Such a photothermographic material includes a reducible non-photosensitive silver source (for example, an organic silver salt), a catalytic amount of a photocatalyst (for example, silver halide),
And a reducing agent for silver are usually contained in a state dispersed in an organic binder matrix. The photosensitive material is stable at room temperature, but when heated to a high temperature (for example, 80 ° C. or higher) after exposure, silver is reduced through a redox reaction between a reducible silver source (which functions as an oxidizing agent) and a reducing agent. Generate. This oxidation-reduction reaction is promoted by the catalytic action of the latent image formed by the exposure. The silver formed by the reaction of the reducible silver salt in the exposed areas becomes black and forms an image because it contrasts with the unexposed areas.

On the other hand, the most common method of forming a color image for a photographic light-sensitive material is a method utilizing a coupling reaction between a coupler and an oxidized developing agent. JP-A-9-10506,
In EP 762,201, a small amount of water is supplied to a photosensitive member containing a developing agent and a coupler, and the photosensitive member is bonded to an image receiving member containing a base precursor, and heated to cause a development reaction, thereby producing color in the photosensitive material. A method for obtaining an image is described. U.S. Pat.Nos. 3,761,270 and 4,021,240
No. 4,426,441, No. 4,435,499, JP-A-59-231
No. 539, and No. 60-128438 disclose a heat-developable color photosensitive material that forms an image only by heating without taking a complicated structure such as a base precursor or a small amount of water. In these patents, p-sulfonamidophenol, ureidoaniline, sulfonylhydrazone and the like are used as developing agents. It is considered that the light-sensitive material of the coupling method is advantageous in terms of sensitivity because the coupler does not absorb light in the visible region before processing, and has an advantage that it can be used not only as a printing material but also as a photographic material.

However, in the case of a multi-layered multilayer color light-sensitive material using these developing agents and couplers, when an oxidized form of the developing agent generated in one layer diffuses into another adjacent layer having different color sensitivity. In addition, color mixing that causes unintended color development becomes a problem. In conventional silver halide color photographic materials, diffusion-resistant hydroquinones generally used for the purpose of preventing color mixing during processing are known, and known hydroquinones are used in photothermographic materials. It was found that when used, it not only has little effect of preventing color mixing, but also greatly promotes fogging during processing. Furthermore, when these hydroquinones are used in a photothermographic material using an organic silver salt as a silver supply source, fogging may occur due to an unexpected reaction between the organic silver salt and silver halide during raw storage. It was found that there was an adverse effect that the developing activity was reduced and the amount of the coloring dye was reduced.

[0005]

SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to provide a simple and rapid processing, especially a high-color saturation color with little color mixing without increasing fog and deteriorating raw storage stability in a heat development system. An object of the present invention is to provide a silver halide color photographic light-sensitive material capable of forming an image, and an image forming method using the same.

[0006]

Means for Solving the Problems In view of the above problems, as a result of intensive studies, the present inventors have found that a heat development method comprising a support having thereon a photosensitive layer containing a photosensitive silver halide, a reducible silver salt and a binder. In the photosensitive material, a color developing agent represented by the following general formula (I) on the photosensitive layer side of the support, a coupler that reacts with the color developing agent to form a dye, and a general formula (SC-1) or a general formula By containing at least one of the compounds represented by formula (SC-2), a color image of high color saturation with little color mixing without deterioration of raw preservability without increasing fog in the heat development system Have been found, and the present invention has been made.

That is, the photothermographic material of the present invention comprises at least (a) a photosensitive silver halide, (b) a reducible silver salt, (c) a compound represented by the following general formula (I) A) a color developing agent represented by (d), a coupler that reacts with the color developing agent to form a dye, (e) represented by the following general formula (SC-1) or the following general formula (SC-2) At least one of the compounds, and
(f) It is characterized by containing a binder.

[0008]

Embedded image (In the general formula (I), R ₁ , R ₂ , R ₃ and R ₄ each independently represent a hydrogen atom or a substituent, and R ₅ and R ₆ each independently represent a substituted or unsubstituted alkyl group, aryl Represents a group, a heterocyclic group, an acyl group, an alkylsulfonyl group or an arylsulfonyl group, R ₁ and R ₂ , R ₃ and R ₄ , R ₅ and R ₆ , R ₂ and R ₅
And / or R ₄ and R ₆ are bonded to each other to form a 5-, 6-, or 7-member
It may form a member ring. R ₇ is R ₁₁ -O-CO-, R ₁₂ -CO-CO
-, R ₁₃ -NH-CO-, R ₁₄ -SO _2- , R ₁₅ -WC (R ₁₆ ) (R ₁₇ )-[W represents an oxygen atom, a sulfur atom or> NR ₁₈ ], R ₁₉ -SO ₂ -NH-
CO- or (M ₁ ) _{1 / n} OSO _2- , R ₁₁ , R ₁₂ , R ₁₃ , R ₁₄ and R
₁₉ represents a substituted or unsubstituted alkyl group, an aryl group, or a heterocyclic group, R ₁₅ represents a hydrogen atom or a block group, R ₁₆ , R ₁₇ and R ₁₈ are a hydrogen atom or a substituted or unsubstituted alkyl group And M ₁ represents an n-valent cation. )

[0009]

Embedded image (In the general formula (SC-1), R ₂₁ represents a hydrogen atom or a substituent, and R ₂₂ represents a substituted or unsubstituted alkyl group, alkenyl group, alkynyl group, aryl group, heterocyclic group, alkoxycarbonyl group, aryl Represents an oxycarbonyl group or a carbamoyl group, R ₂₃ represents a hydrogen atom, a substituted or unsubstituted alkyl group, an alkenyl group, an alkynyl group, an aryl group or a heterocyclic group, and in the general formula (SC-2), R ₂₄ represents a substituted Or an unsubstituted alkyl group, alkenyl group, alkynyl group, aryl group, heterocyclic group, alkoxy group, aryloxy group, heterocyclic oxy group, amino group or anilino group, R ₂₅ is a substituted or unsubstituted alkoxycarbonyl group, an aryloxycarbonyl group, or carbamoyl group, R ₂₆ is a substituted or unsubstituted alkyl group, an alkenyl group, an alkynyl group, an aryl Or it represents a heterocyclic group.
R ₂₄ and R ₂₆ may combine to form a 5- to 7-membered ring. )

In the present invention, by further satisfying the following conditions, a more excellent photothermographic material can be obtained.

(1) R _{7 of the} color developing agent represented by the general formula (I) is preferably represented by the following formula (T-1). BLK-W- (X = Y) _j -C (R ₃₁ ) (R ₃₂ ) -O-CO- (T-1) (In the formula (T-1), BLK represents a block group, and W Represents an oxygen atom, a sulfur atom or> NR ₃₃ ; X and Y each represent a substituted or unsubstituted methine or nitrogen atom;
Or R 2, and R ₃₁ , R ₃₂ and R ₃₃ each represent a hydrogen atom or a substituent. )

(2) The above components (a) to
It is preferable to contain a compound that releases a base or a nucleophile by heat on the same surface as that containing (f).

(3) The reducible silver salt is preferably a compound having a triazole group.

(4) When the photothermographic material of the present invention is used for color photography, at least three kinds of silver halide photosensitive layers having different spectral sensitivities are provided, and a non-photosensitive layer between the photosensitive layers has the general formula ( It is preferable to use at least one compound selected from the group consisting of (SC-1) and the general formula (SC-2).

(5) The photothermographic material of the present invention preferably has a silver halide emulsion layer containing 50% or more of silver halide tabular grains having an aspect ratio of 8 to 50.

(6) The photothermographic material of the present invention preferably contains a compound represented by the following general formula (F-1) or (F-2).

Embedded image (In the general formula (F-1), R _f1 represents an alkyl group having 4 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or an aralkyl group having 7 to 20 carbon atoms, and M ₂ represents a hydrogen atom or a cation. Represents.)

Embedded image (In the general formula (F-2), R _f2 is a hydrogen atom, and has 4 to 20 carbon atoms.
Represents an alkyl group, an aryl group having 6 to 20 carbon atoms, or an aralkyl group having 7 to 20 carbon atoms, and R _f3 represents an alkyl group having 4 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or a carbon atom having 7 carbon atoms. ~
An aralkyl group of 20, M ₂ represents a hydrogen atom or a cation. However, the total number of carbon atoms of R _f2 and R _f3 is 4 to 30. )

(7) The compound represented by the formula (F-1) or (F-2) is preferably a metal salt which is hardly soluble in water.

(8) After the imagewise exposure of the photothermographic material of the present invention, the photothermographic material is heated at a temperature of 60 ° C. to 180 ° C. for 5 to 60 seconds to form a color image. It is preferable that the read image information is photoelectrically read and an image is formed on another recording material based on the image information.

[0019]

BEST MODE FOR CARRYING OUT THE INVENTION [I] Photothermographic Material The photothermographic material of the present invention has a photosensitive layer containing an organic silver salt as a reducible silver salt and a binder on a support. On the upper photosensitive layer side, a color developing agent represented by the general formula (I), a coupler that reacts with the color developing agent to form a dye, and a compound represented by the general formula (SC-1) or the general formula (SC-2) It is characterized by containing at least one of the compounds represented.

The photothermographic material of the present invention has at least three different photosensitive wavelength ranges and / or different absorption wavelength ranges of the dyes formed from the color developing agent of formula (I) and the coupler.
By providing a kind of photosensitive silver halide emulsion layer (photosensitive layer), a dye image can be obtained.

Formula (I) contained in the photothermographic material of the present invention
Is a compound that has little absorption in the visible region, but releases a reducing agent upon thermal development or contributes itself to forming a silver image by acting as a reducing agent, and the released reduced An oxidized form of the agent, or an oxidized form of itself, is formed. When these oxidized products react with the coupler compound, a dye is formed, and an imagewise dye image corresponding to a silver image is obtained. In the present invention, the dye-providing coupler and the color developing agent (or a precursor thereof) may be contained in the photosensitive layer, but may be separately added to another layer as long as it can react.

When the reducing agent released from the compound of formula (I) or the oxidized form of the compound itself diffuses into an adjacent layer having different color sensitivity and reacts there with a coupler to form a dye, an unintended color formation occurs. As a result, the saturation of the color image is reduced due to the color mixture. Therefore, an intermediate layer is provided between the photosensitive layers having different color sensitivities, and the compounds of the general formulas (SC-1) and (SC-2) lose the oxidized form of the compound of the formula (I) diffused into other layers. By making use of
Color mixing can be prevented. Compounds of general formulas (SC-1) and (SC-2)
It may be contained in the same layer or a layer adjacent to the color developing agent, but is preferably contained in a non-photosensitive layer between each photosensitive layer.

[A] Color Developing Agent of the General Formula (I) The color developing agent of the general formula (I) is a compound having almost no absorption in the visible region. Then, the reducing agent is released, or acts as a reducing agent itself, thereby contributing to the formation of a silver image, and an oxidized form of the released reducing agent or an oxidized form of itself is generated.
When these oxidized products react with the coupler compound, a dye is formed, and an imagewise dye image corresponding to a silver image is obtained.

[0024]

Embedded image

R ₁ , R ₂ , R ₃ and R ₄ each independently represent a hydrogen atom or a substituent. Examples of the substituent represented by R ₁ , R ₂ , R ₃ and R ₄ include a halogen atom (for example, a chlorine atom, a bromine atom, an iodine atom), an alkyl group [linear, branched, cyclic substituted or unsubstituted alkyl Represents a group. An alkyl group (preferably an alkyl group having 1 to 30 carbon atoms such as methyl, ethyl, n-propyl, isopropyl, t-butyl, n-octyl, eicosyl, 2-chloroethyl, 2-cyanoethyl, 2-
Ethylhexyl), a cycloalkyl group (preferably a substituted or unsubstituted cycloalkyl group having 3 to 30 carbon atoms, for example, cyclohexyl, cyclopentyl, 4-n-dodecylcyclohexyl), a bicycloalkyl group (preferably substituted with 5 to 30 carbon atoms) Or an unsubstituted bicycloalkyl group, that is, a monovalent group obtained by removing one hydrogen atom from a bicycloalkane having 5 to 30 carbon atoms, for example, bicyclo [1,2,
2] heptane-2-yl, bicyclo [2,2,2] octan-3-yl), and also includes a tricyclo structure having many ring structures.
An alkyl group (for example, an alkyl group of an alkylthio group) among the substituents described below also represents an alkyl group having such a concept. An alkenyl group [which represents a linear, branched, or cyclic substituted or unsubstituted alkenyl group; An alkenyl group (preferably a substituted or unsubstituted alkenyl group having 2 to 30 carbon atoms, for example, vinyl, allyl, prenyl, geranyl, oleyl), a cycloalkenyl group (preferably having 3 to 30 carbon atoms);
It is a 30-substituted or unsubstituted cycloalkenyl group, that is, a monovalent group obtained by removing one hydrogen atom from a cycloalkene having 3 to 30 carbon atoms. For example, 2-cyclopentene-1
-Yl, 2-cyclohexen-1-yl), bicycloalkenyl group (substituted or unsubstituted bicycloalkenyl group, preferably substituted or unsubstituted bicycloalkenyl group having 5 to 30 carbon atoms, that is, bicyclo having one double bond A monovalent group obtained by removing one hydrogen atom from an alkene, for example, bicyclo [2,2,1] hept-2-en-1-yl, bicyclo
[2,2,2] oct-2-en-4-yl)], alkynyl group (preferably substituted or unsubstituted alkynyl group having 2 to 30 carbon atoms, for example, ethynyl, propargyl, trimethylsilylethynyl group), aryl group (Preferably 6 to 30 carbon atoms
A substituted or unsubstituted aryl group such as phenyl,
One hydrogen atom from a p-tolyl, naphthyl, m-chlorophenyl, o-hexadecanoylaminophenyl), heterocyclic group (preferably a 5- or 6-membered substituted or unsubstituted aromatic or non-aromatic heterocyclic compound) And more preferably a 5- or 6-membered aromatic heterocyclic group having 3 to 30 carbon atoms, for example, 2-furyl,
2-thienyl, 2-pyrimidinyl, 2-benzothiazolyl),
Cyano group, hydroxy group, nitro group, carboxyl group,
Alkoxy group (preferably substituted or unsubstituted alkoxy group having 1 to 30 carbon atoms, for example, methoxy, ethoxy,
Isopropoxy, t-butoxy, n-octyloxy, 2-methoxyethoxy), aryloxy group (preferably substituted or unsubstituted aryloxy group having 6 to 30 carbon atoms,
For example, phenoxy, 2-methylphenoxy, 4-t-butylphenoxy, 3-nitrophenoxy, 2-tetradecanoylaminophenoxy), silyloxy group (preferably silyloxy group having 3 to 20 carbon atoms, such as trimethylsilyloxy, t-butyl) Dimethylsilyloxy), a heterocyclic oxy group (preferably a substituted or unsubstituted heterocyclic oxy group having 2 to 30 carbon atoms, 1-phenyltetrazole-5-oxy, 2-tetrahydropyranyloxy), an acyloxy group (preferably Formyloxy group, substituted or unsubstituted alkylcarbonyloxy group having 2 to 30 carbon atoms, substituted or unsubstituted arylcarbonyloxy group having 6 to 30 carbon atoms, for example, formyloxy, acetyloxy, pivaloyloxy, stearoyloxy, benzoyloxy , P-methoxyphenylcarbo Carbamoyloxy group (preferably substituted or unsubstituted carbamoyloxy group having 1 to 30 carbon atoms such as N, N-dimethylcarbamoyloxy, N, N-diethylcarbamoyloxy, morpholinocarbonyloxy, N, N-di -n-octylaminocarbonyloxy, Nn-octylcarbamoyloxy), alkoxycarbonyloxy group (preferably substituted or unsubstituted alkoxycarbonyloxy group having 2 to 30 carbon atoms, for example, methoxycarbonyloxy, ethoxycarbonyloxy, t-butoxycarbonyl Oxy, n-
Octylcarbonyloxy), an aryloxycarbonyloxy group (preferably a substituted or unsubstituted aryloxycarbonyloxy group having 7 to 30 carbon atoms, such as phenoxycarbonyloxy, p-methoxyphenoxycarbonyloxy, pn-hexadecyloxyphenoxycarbonyloxy ), An amino group (preferably an amino group, a substituted or unsubstituted alkylamino group having 1 to 30 carbon atoms,
A substituted or unsubstituted anilino group having 6 to 30 carbon atoms, for example, amino, methylamino, dimethylamino, anilino, N-methyl-anilino, diphenylamino), an acylamino group (preferably formylamino group,
30 substituted or unsubstituted alkylcarbonylamino groups and substituted or unsubstituted arylcarbonylamino groups having 6 to 30 carbon atoms, such as formylamino, acetylamino, pivaloylamino, lauroylamino, benzoylamino, 3,4,5-tri -n-octyloxyphenylcarbonylamino), aminocarbonylamino group (preferably substituted or unsubstituted aminocarbonylamino having 1 to 30 carbon atoms, such as carbamoylamino, N, N-dimethylaminocarbonylamino, N, N-diethylamino Carbonylamino, morpholinocarbonylamino), alkoxycarbonylamino group (preferably substituted or unsubstituted alkoxycarbonylamino group having 2 to 30 carbon atoms, for example, methoxycarbonylamino, ethoxycarbonylamino, t-butoxycarbonylamino n-octadecyloxycarbonylamino, N-methylmethoxycarbonylamino), aryloxycarbonylamino group (preferably substituted or unsubstituted aryloxycarbonylamino group having 7 to 30 carbon atoms, for example, phenoxycarbonylamino, p-chlorophenoxycarbonyl Amino, mn-octyloxyphenoxycarbonylamino), sulfamoylamino group (preferably substituted or unsubstituted sulfamoylamino group having 0 to 30 carbon atoms, for example, sulfamoylamino, N, N-dimethylaminosulfonylamino , Nn-
Octylaminosulfonylamino), alkyl and arylsulfonylamino groups (preferably substituted or unsubstituted alkylsulfonylamino having 1 to 30 carbon atoms, substituted or unsubstituted arylsulfonylamino having 6 to 30 carbon atoms such as methylsulfonylamino, Butylsulfonylamino, phenylsulfonylamino, 2,3,5-trichlorophenylsulfonylamino, p-methylphenylsulfonylamino), mercapto group, alkylthio group (preferably substituted or unsubstituted alkylthio group having 1 to 30 carbon atoms, for example, Methylthio, ethylthio, n-hexadecylthio), arylthio groups (preferably having 6 to 30 carbon atoms)
A substituted or unsubstituted arylthio such as phenylthio, p-chlorophenylthio, m-methoxyphenylthio), a heterocyclic thio group (preferably a substituted or unsubstituted heterocyclic thio group having 2 to 30 carbon atoms such as 2-benzo) Thiazolylthio, 1-phenyltetrazol-5-ylthio), sulfamoyl group (preferably substituted or unsubstituted sulfamoyl group having 0 to 30 carbon atoms, for example, N-ethylsulfamoyl, N- (3-dodecyloxypropyl) Sulfamoyl, N, N-dimethylsulfamoyl, N-acetylsulfamoyl, N-benzoylsulfamoyl, N- (N′-phenylcarbamoyl) sulfamoyl), sulfo group, alkyl and arylsulfinyl group (preferably having carbon atoms From 1
30 substituted or unsubstituted alkylsulfinyl groups, from 6
30 substituted or unsubstituted arylsulfinyl groups such as methylsulfinyl, ethylsulfinyl, phenylsulfinyl, p-methylphenylsulfinyl), alkyl and arylsulfonyl groups (preferably having 1 to
30 substituted or unsubstituted alkylsulfonyl groups, 6 to 30
A substituted or unsubstituted arylsulfonyl group such as methylsulfonyl, ethylsulfonyl, phenylsulfonyl, p-methylphenylsulfonyl), an acyl group (preferably a formyl group, a substituted or unsubstituted alkylcarbonyl group having 2 to 30 carbon atoms), A substituted or unsubstituted arylcarbonyl group having 7 to 30 carbon atoms, for example, acetyl, pivaloyl, 2-chloroacetyl, stearoyl, benzoyl, pn-octyloxyphenylcarbonyl, an alkoxycarbonyl group (preferably having 2 to 30 carbon atoms) Or an unsubstituted alkoxycarbonyl group such as methoxycarbonyl, ethoxycarbonyl, t-butoxycarbonyl, n-octadecyloxycarbonyl), an aryloxycarbonyl group (preferably a substituted or unsubstituted aryloxycarbonyl group having 7 to 30 carbon atoms) Boniru group, e.g. phenoxycarbonyl, o- chlorophenoxy carbonyl, m-
Nitrophenoxycarbonyl, pt-butylphenoxycarbonyl), carbamoyl group (preferably having 1 carbon atom)
30 substituted or unsubstituted carbamoyls such as carbamoyl, N-methylcarbamoyl, N, N-dimethylcarbamoyl, N, N-di-n-octylcarbamoyl, N- (methylsulfonyl) carbamoyl), aryl and heterocyclic azo groups (Preferably a substituted or unsubstituted arylazo group having 6 to 30 carbon atoms, a substituted or unsubstituted heterocyclic azo group having 3 to 30 carbon atoms, for example, phenylazo, p-chlorophenylazo, 5-ethylthio-1,3,4 -Thiadiazol-2-ylazo), imide group (preferably N-succinylimide, N-phthalimide), phosphino group (preferably having 2 carbon atoms)
30 substituted or unsubstituted phosphino groups such as dimethylphosphino, diphenylphosphino, methylphenoxyphosphino), phosphinyl group (preferably having 2 carbon atoms)
To 30 substituted or unsubstituted phosphinyl groups such as phosphinyl, dioctyloxyphosphinyl, diethoxyphosphinyl), and phosphinyloxy groups (preferably substituted or unsubstituted phosphinyloxy having 2 to 30 carbon atoms) Groups such as diphenoxyphosphinyloxy, dioctyloxyphosphinyloxy), phosphinylamino groups (preferably substituted or unsubstituted phosphinylamino groups having 2 to 30 carbon atoms, such as dimethoxyphosphinylamino, Dimethylaminophosphinylamino) and a silyl group (preferably a substituted or unsubstituted silyl group having 3 to 30 carbon atoms, for example, trimethylsilyl, t-butyldimethylsilyl, phenyldimethylsilyl).

R _{1 to} R ₄ are hydrogen, halogen, alkyl, aryl, cyano, hydroxy, nitro, carboxyl, alkoxy, aryloxy, acyloxy, acylamino, alkyl and arylsulfonyl An amino group, an alkylthio group, an arylthio group, a sulfamoyl group, a sulfo group, an acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a carbamoyl group, an alkylsulfonyl group and an arylsulfonyl group are preferable, and a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group Group, acylamino group, alkyl and arylsulfonylamino group, alkylthio group, arylthio group, sulfamoyl group, sulfo group, alkoxycarbonyl group, carbamoyl group, alkylsulfonyl group and arylsulfonyl group Is more preferred. Particularly preferably, in R _{1 to} R ₄ , _one of R _{1 and} R ₃ is a hydrogen atom.

[0027] When the group represented by R ₁ to R ₄ is a group capable of being further substituted, the group represented by R ₁ to R ₄ may further have a substituent group, preferred substituents when the Represents the same group as the substituent described for R _{1 to} R ₄ . When substituted by two or more substituents, those substituents may be the same or different.

R ₅ and R ₆ are each independently an alkyl group,
Represents an aryl group, a heterocyclic group, an acyl group, an alkylsulfonyl group or an arylsulfonyl group, and the preferred range of these groups is the alkyl group or the aryl group described in the substituents represented by R _{1 to} R ₄ above. , A heterocyclic group, an acyl group, an alkylsulfonyl group and an arylsulfonyl group. R ₅ and R ₆ are preferably an alkyl group, an aryl group and a heterocyclic group, and most preferably an alkyl group. R ₅
And when the group represented by R ₆ is a group capable of being further substituted, R ₅
And groups represented by R ₆ may further have a substituent, preferable substituent is the same as the substituents described in the R ₁ to R _4. When substituted with two or more substituents,
These substituents may be the same or different.

R ₁ and R ₂ , R ₃ and R ₄ , R ₅ and R ₆ , R ₂ and R ₅ and R ₄
In one or more of the sets of R ₆ , the R groups may be bonded to each other to form a 5-, 6-, or 7-membered ring.

R in the general formula (I)₇Is R₁₁-O-CO-, R₁₂-CO
-CO-, R₁₃-NH-CO-, R₁₄-SO_Two-, R_Fifteen-W-C (R₁₆) (R₁₇)-[W
Is an oxygen atom, a sulfur atom or> N-R₁₈Represents], R₁₉-SO_Two
-NH-CO- or (M₁)_{1 / n}OSO_Two-Represents R₁₁, R₁₂, R₁₃, R₁₄
And R₁₉Is a substituted or unsubstituted alkyl group, aryl group,
Or represents a heterocyclic group, R_FifteenIs a hydrogen atom or a block group
And R₁₆, R₁₇And R₁₈Is a hydrogen atom or substituted or absent
Represents a substituted alkyl group, M ₁Represents an n-valent cation.

The alkyl group, aryl group and heterocyclic group represented by R ₁₁ , R ₁₂ , R ₁₃ , R ₁₄ and R ₁₉ are the same as those described above for R _{1 to} R ₄
May be the same as the alkyl group, aryl group and heterocyclic group described for the substituent represented by. R ₁₁ , R ₁₂ , R ₁₃ , R ₁₄ and R
_{When the} group represented by ₁₉ is a further substitutable group, it may further have a substituent, and in that case, a preferable substituent is R ₁ to
It may be the same as the substituent described in the explanation of R _4. When substituted by two or more substituents, those substituents may be the same or different. When R ₁₆ , R ₁₇ and R ₁₈ represent an alkyl group, they represent the same groups as the alkyl groups described for the substituents represented by R _{1 to} R ₄ . When R ₁₅ represents a blocking group, the blocking group is the same as the blocking group represented by BLK described below.

R ₇ is R ₁₁ -O-CO-, R ₁₄ -SO _2- , R ₁₅ -WC
(R ₁₆ ) (R ₁₇ )-and R ₁₉ -SO ₂ -NH-CO- are preferred, and R ₁₁ -O-CO-
And R ₁₉ -SO ₂ -NH-CO- are more preferred. R ₁₁ is preferably an alkyl group, R ₁₂ and R ₁₃ are preferably an alkyl group and an aryl group, and R ₁₄ is preferably an aryl group. Particularly preferred is R ₁₁ -O-CO-, wherein R ₁₁ is an alkyl group, and the timing at which a cleavage reaction is caused by utilizing an electron transfer reaction described in U.S. Pat.No. 4,409,323 or 4,421,845. It is preferably a group containing a group, and it is preferable that the terminal that causes the electron transfer reaction of the timing group is blocked. Such R ₇ is represented by the following formula (T-1).

BLK-W- (X = Y)_j-C (R₃₁) (R₃₂) -O-CO- (T-1) In the formula (T-1), BLK represents a blocking group, and W is an oxygen atom.
Child, sulfur atom or> N-R ₃₃X and Y are each methyl
Represents a nitrogen atom or a nitrogen atom; j represents 0, 1 or 2; ₃₁,
R₃₂And R₃₃Is a hydrogen atom or R₁~ R_FourSubstituents described in
Represents the same group as Where X and Y represent substituted methine
When the substituent, R₃₁, R₃₂And R₃₃Any two of each
Are linked to form a cyclic structure (eg, a benzene ring,
(A azole ring).

As the block group represented by BLK, known groups can be used. For example, Japanese Patent Publication No. 48-9968,
Nos. 2-8828, 57-82834, U.S. Pat. No. 3,311,476 and Japanese Patent Publication No. 47-44805 (U.S. Pat.No. 3,615,617) described in, for example, acyl groups, sulfonyl groups, and other blocking groups. 17369 (U.S. Patent No. 3,888,677), 55-9696
Nos. (U.S. Pat.No. 3,791,830), U.S. Pat. No. 5,049,027 (U.S. Pat.No. 4,009,029), and JP-A-56-77842 (U.S. Pat.
No. 07,175), No. 59-105640, No. 59-105641, and No. 59-1
No. 05642, a blocking group utilizing the reverse Michael reaction described in JP-B-54-39727, U.S. Pat.
No. 3,932,480, No. 3,993,661, JP-A-57-135944
Nos. 57-135945 (U.S. Pat.No. 4,420,554), 57-1
Nos. 36640, 61-196239, 61-196240 (U.S. Pat.
Utilization of quinone methide or a compound similar to quinone methide by intramolecular electron transfer described in JP-A Nos. 4,702,999, 61-185743, 61-124941 (US Pat. No. 4,639,408) and JP-A-2-280140. Nos. 4,358,525 and 4,330,617, JP-A-55-53330 (US Pat. No. 4,310,612), 59-121328, and 59-218
Nos. 439 and 63-318555 (European Patent No. 0295729)
And the like. A blocking group utilizing an intramolecular nucleophilic substitution reaction described in JP-A-57-76541 (US Pat. No. 4,335,200)
No. 57-135949 (U.S. Pat.No. 4,350,752) and No. 57
-179842, 59-137945, 59-140445, 59-2197
Nos. 41, 59-202459 and 60-41034 (U.S. Pat.
No. 8,563), No. 62-59945 (US Pat. No. 4,888,268),
Nos. 62-65039 (U.S. Pat.No. 4,772,537) and 62-80647
JP-A-59-201057 (US Pat. No. 4,518,685), a block group utilizing a ring-cleaving reaction of a 5- or 6-membered ring described in JP-A-3-236047 and JP-A-3-238445. ),same
61-43739 (U.S. Pat.No. 4,659,651), 61-95346 (U.S. Pat.No. 4,690,885), 61-95347 (U.S. Pat.No. 4,892,811), JP-A-64-7035, JP-A-4-42650 No. (U.S. Pat.No. 5,066,573), JP-A-1-245255, JP-A-2-20724
Nos. 9 and 2-35055 (US Pat. No. 5,118,596) and 4-
No. 186344, a blocking group utilizing an addition reaction of a nucleophile to a conjugated unsaturated bond described in JP-A-59-93442,
Nos. 61-32839, 62-163051 and block groups utilizing a β-elimination reaction described in JP-B-5-37299, etc., and diarylmethanes described in JP-A-61-188540. A block group utilizing a nucleophilic substitution reaction of
No. 0, JP-A-62-80646, JP-A-62-144163 and JP-A-62-147457.
No. 4,078,098, a block group utilizing a reaction between an N-acyl compound of thiazolidine-2-thione and an amine described in
2-296240 (U.S. Pat.No. 5,019,492), 4-177243
Nos. 4-177244, 4-177245, 4-177246, 4-
177247, 4-177248, 4-177249, 4-179948
No. 4-184337, No. 4-184338, WO92 / 21064, JP-A-4-330438, WO93 / 03419 and JP-A-5-45816 described two electrophilic groups. And a blocking group which reacts with a dinucleophile, and JP-A-3-236047 and JP-A-3-238445. Of these blocking groups, particularly preferred are those described in JP-A-2-296240 (US Pat. No. 5,019,491).
No. 2), No. 4-177243, No. 4-177244, No. 4-177245,
4-177246, 4-177247, 4-177248, 4-177
No. 49, No. 4-179948, No. 4-184337, No. 4-184338, WO
92/21064, JP-A-4-330438, WO93 / 03419 and JP-A-5-45816 are block groups having two electrophilic groups and reacting with a dinucleophile. .

Specific examples of the timing group portion obtained by removing BLK from the group represented by the formula (T-1) include the following. In the following, * indicates a position that binds to BLK,
** represents a position that binds to -O-CO-.

[0036]

[Formula 10]

Specific examples of the compounds of the color developing agent represented by the formula (I) of the present invention are shown below, but the present invention is not limited thereto.

[0038]

[Formula 11]

[0039]

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[0040]

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[0041]

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[0042]

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[0043]

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[0044]

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[0045]

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[0046]

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As the color developing agent represented by the formula (I) used in the present invention, US Pat. Nos. 5,242,783 and 4,426,441;
JP-A-62-227141, JP-A-5-257225, JP-A-5-249602
And compounds described in JP-A Nos. 6-43607 and 7-333780 are also preferable. The present invention includes European Patent No. 1,113,
No. 322, No. 1,113,323, No. 1,113,324, No. 1,113,325
And the developing agents described in JP-A Nos. 1,113,326 can also be preferably used.

The amount of the color developing agent represented by the formula (I) can be added in a wide range.
l-fold is preferred, and 0.1-10 mol-fold is more preferred.

The color developing agent represented by the formula (I) is a solution,
The powder, solid fine particle dispersion, emulsion, oil protection dispersion and the like may be added to the coating solution by any method. Dispersion of the solid fine particles is carried out by a known fine means (for example, ball mill, vibrating ball mill, sand mill, colloid mill, jet mill, roller mill, etc.). When dispersing the solid fine particles, a dispersing aid may be used.

The photothermographic material of the present invention may contain a reducing agent in addition to the color developing agent of the formula (I). In addition to conventional photographic developers such as phenidone, hydroquinone and catechol, hindered phenol reducing agents can also be mentioned as preferred examples. The reducing agent is preferably contained in an amount of 5 to 50 mol%, more preferably 10 to 40 mol%, per 1 mol of silver on the surface having the photosensitive layer. The layer to which the reducing agent is added may be any layer on the photosensitive layer side with respect to the support. When added to a layer other than the photosensitive layer, it is preferable to use a relatively large amount of 10 to 50 mol% with respect to 1 mol of silver. The reducing agent may be a so-called precursor which is derivatized so as to have a function effectively only during development.

In the photothermographic material using an organic silver salt, a wide range of reducing agents can be used. For example, JP 46-6074, JP 47-1238, JP 47-33621, JP
49-46427, 49-115540, 50-14334, 50-3611
No. 0, No. 50-147711, No. 51-32632, No. 51-1023721,
No. 51-32324, No. 51-51933, No. 52-84727, No. 55-108
654, 56-146133, 57-82828, 57-82829,
JP-A-6-3793, U.S. Patent No. 3,667,9586, No. 3,679,
No. 426, No. 3,751,252, No. 3,751,255, No. 3,76
No. 1,270, No. 3,782,949, No. 3,839,048, No. 3,9
No. 28,686, No. 5,464,738, German Patent No. 2,321,328,
The reducing agent disclosed in European Patent Publication No. 692,732 or the like can be used.

Specific examples include amide oximes such as phenylamide oxime, 2-thienylamide oxime and p-phenoxyphenylamide oxime; azines such as 4-hydroxy-3,5-dimethoxybenzaldehyde azine; A combination of an aliphatic carboxylic acid arylhydrazide and ascorbic acid, such as a combination of bis (hydroxymethyl) propionyl-β-phenylhydrazine and ascorbic acid; a combination of polyhydroxybenzene and hydroxyamine, reductone and / or hydrazine (eg, Hydroquinone, bis (ethoxyethyl) hydroxyamine, piperidinohexose reductone or formyl-4
A combination of azine and sulfonamidophenol (for example, phenothiazine and 2,6-dichloro-4); a hydroxamic acid such as phenylhydroxamic acid, p-hydroxyphenylhydroxamic acid and β-alinine hydroxamic acid; Α-cyanophenylacetic acid derivatives such as ethyl-α-cyano-2-methylphenylacetate and ethyl-α-cyanophenylacetate; 2,2′-dihydroxy-
1,1'-binaphthyl, 6,6'-dibromo-2,2'-dihydroxy-
1,1'-binaphthyl and bis (2-hydroxy-1-naphthyl)
Bis-β-naphthol as exemplified by methane; bis-
Combination of β-naphthol and a 1,3-dihydroxybenzene derivative (eg, 2,4-dihydroxybenzophenone or 2,4-dihydroxyacetophenone); 5-pyrazolone such as 3-methyl-1-phenyl-5-pyrazolone; dimethylamino Hexose reductone, reductone as exemplified by anhydrodihydroaminohexose reductone and anhydrodihydropiperidone hexose reductone; 2,6-
Dichloro-4-benzenesulfonamidophenol and p-
Sulfonamidophenol reducing agents such as benzenesulfonamidophenol; 2-phenylindan-1,3-dione; chromanes such as 2,2-dimethyl-7-tert-butyl-6-drocycloman; 2,6-dimethoxy -3,5-dicarbethoxy-
1,4-dihydropyridines such as 1,4-dihydropyridine; bisphenols (for example, bis (2-hydroxy-3-tert-butyl-
5-methylphenyl) methane, 2,2-bis (4-hydroxy-3-
Methylphenyl) propane, 4,4-ethylidenebis (2-tert
-Butyl-6-methylphenol), 1,1-bis (2-hydroxy
(-3,5-dimethylphenyl) -3,5,5-trimethylhexane,
And 2,2-bis (3,5-dimethyl-4-hydroxyphenyl) propane, etc.); ascorbic acid derivatives (eg, 1-ascorbyl palmitate, ascorbyl stearate, etc.); and aldehydes and ketones such as benzyl and biacetyl; -Pyrazolidone and certain indan-1,3-diones; chromanol (such as tocopherol) and the like.

[B] Color mixing inhibitor of general formulas (SC-1) and (SC-2) The reducing agent released from the color developing agent of general formula (I) or an oxidized product of itself is adjacent to the color developing agent. When it diffuses into layers of different color sensitivity, where it reacts with the coupler to form a dye,
Unintended color development occurs, and the saturation of a color image is reduced due to color mixing. Therefore, by using a compound of the general formula (SC-1) or (SC-2) in the same layer or an adjacent layer with the color developing agent, the oxidized form of the compound of the formula (I) diffused into other layers is deactivated. To prevent color mixing.

[0054]

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First, the compound represented by formula (SC-1) will be described in detail. In the general formula (SC-1), R ₂₁ represents a hydrogen atom or a substituent, and specifically, a hydrogen atom, a halogen atom (for example, a fluorine atom, a chlorine atom, or a bromine atom), an alkyl group (preferably having 1 to 32 carbon atoms) Straight, branched or cyclic alkyl group such as methyl, ethyl, propyl, isopropyl, butyl, t-butyl, 1-octyl, tridecyl, cyclopropyl, cyclopentyl, cyclohexyl, 1-norbornyl, 1-adamantyl), alkenyl A group (preferably an alkenyl group having 2 to 32 carbon atoms, for example, vinyl, allyl, 3-buten-1-yl), an alkynyl group (preferably an alkynyl group having 2 to 32 carbon atoms, for example, ethynyl, 1-propynyl) An aryl group (preferably an aryl group having 6 to 32 carbon atoms such as phenyl, 1-naphthyl and 2-naphthyl), a heterocyclic group (preferably having 1 carbon atom). 32 to a 5- to 8-membered heterocyclic group, for example, 2-thienyl,
4-pyridyl, 2-furyl, 2-pyrimidinyl, 1-pyridyl,
2-benzothiazolyl, 1-imidazolyl, 1-pyrazolyl,
Benzotriazol-2-yl), a silyl group (preferably a silyl group having 3 to 32 carbon atoms, for example, trimethylsilyl,
Triethylsilyl, tocibutylsilyl, t-butyldimethylsilyl, t-hexyldimethylsilyl), a hydroxy group, an alkoxy group (preferably an alkoxy group having 1 to 32 carbon atoms, for example, methoxy, ethoxy, 1-butoxy, 2-butoxy , Isopropoxy, t-butoxy, dodecyloxy, cyclopentyloxy, cyclohexyloxy),
An aryloxy group (preferably an aryloxy group having 6 to 32 carbon atoms such as phenoxy and 2-naphthoxy), a heterocyclic oxy group (preferably a heterocyclic oxy group having 1 to 32 carbon atoms such as 1-phenyltetrazole- 5-oxy, 2-
Tetrahydropyranyloxy, 2-furyloxy), silyloxy group (preferably a silyloxy group having 1 to 32 carbon atoms, for example, trimethylsilyloxy, t-butyldimethylsilyloxy, diphenylmethylsilyloxy), acyloxy group (preferably carbon number 2 to 32 acyloxy groups, for example, acetoxy, pivaloyloxy, benzoyloxy, dodecanoyloxy), alkoxycarbonyloxy group (preferably 2 to 32 carbon atoms, for example, ethoxycarbonyloxy, t-
Butoxycarbonyloxy, cyclohexyloxycarbonyloxy), an aryloxycarbonyloxy group (preferably an aryloxycarbonyloxy group having 7 to 32 carbon atoms such as phenoxycarbonyloxy), a carbamoyloxy group (preferably carbamoyl having 1 to 32 carbon atoms) An oxy group, for example, N, N-dimethylcarbamoyloxy, N-butylcarbamoyloxy), a sulfamoyloxy group (preferably a sulfamoyloxy group having 1 to 32 carbon atoms, for example, N, N-diethylsulfamoyl) Oxy,
N-propylsulfamoyloxy), alkanesulfonyloxy group (preferably an alkanesulfonyloxy group having 1 to 32 carbon atoms, for example, methanesulfonyloxy, hexadecanesulfonyloxy), arene sulfonyloxy group (preferably 6 to 32 carbon atoms) An arenesulfonyloxy group such as benzenesulfonyloxy), a cyano group, an acyl group (preferably an acyl group having 1 to 32 carbon atoms,
For example, formyl, acetyl, pivaloyl, benzoyl,
Tetradecanoyl), an alkoxycarbonyl group (preferably an alkoxycarbonyl group having 2 to 32 carbon atoms, for example, methoxycarbonyl, ethoxycarbonyl, octadecyloxycarbonyl, cyclohexyloxycarbonyl), an aryloxycarbonyl group (preferably having 7 to 32 carbon atoms) An aryloxycarbonyl group such as phenoxycarbonyl) and a carbamoyl group (preferably a carbamoyl group having 1 to 32 carbon atoms such as carbamoyl and N, N-
Dibutylcarbamoyl, N-ethyl-N-octylcarbamoyl, N-propylcarbamoyl), amino group (preferably an amino group having 32 or less carbon atoms, for example, amino, methylamino, N, N-dioctylamino, tetradecylamino, octadecyl) Amino), anilino group (preferably having 6 carbon atoms)
~ 32 anilino groups, for example, anilino, N-methylanilino), a heterocyclic amino group (preferably a 1 to 32 heterocyclic amino group, for example, 4-pyridylamino), a carbonamido group (preferably 2 to 2 carbon atoms) 32 carbonamide groups, for example, acetamido, benzamide, tetradecaneamide), ureido group (preferably a ureido group having 1 to 32 carbon atoms, such as ureido, N, N-dimethylureido,
N-phenylureido), imide group (preferably having 10 carbon atoms)
In the following imide groups, for example, N-succinimide, N-phthalimido), alkoxycarbonylamino group (preferably an alkoxycarbonylamino group having 2 to 32 carbon atoms, for example, methoxycarbonylamino, ethoxycarbonylamino, t-butoxycarbonylamino, Octadecyloxycarbonylamino, cycloalkyloxycarbonylamino), an aryloxycarbonylamino group (preferably an aryloxycarbonylamino group having 7 to 32 carbon atoms, for example, phenoxycarbonylamino), a sulfonamide group (preferably having 1 to 32 carbon atoms) Methanesulfonamide, butanesulfonamide, benzenesulfonamide, hexadecanesulfonamide), sulfamoylamino group (preferably having 1 carbon atom)
~ 32 sulfamoylamino groups, for example, N, N-dipropylsulfamoylamino, N-ethyl-N-dodecylsulfamoylamino), azo group (preferably an azo group having 1 to 32 carbon atoms, e.g., Phenylazo), a nitro group, an alkylthio group (preferably an alkylthio group having 1 to 32 carbon atoms,
For example, ethylthio, octylthio, cycloalkylthio), an arylthio group (preferably an arylthio group having 6 to 32 carbon atoms, for example, phenylthio), a heterocyclic thio group (preferably a heterocyclic thio group having 1 to 32 carbon atoms, for example,
2-benzothiazolylthio, 2-pyridylthio, 1-phenyltetrazolylthio), alkanesulfinyl group (preferably an alkylsulfinyl group having 1 to 32 carbon atoms, for example, dodecanesulfinyl), arene sulfinyl group (preferably 6 carbon atoms) An arenesulfinyl group of, for example, benzenesulfinyl), an alkanesulfonyl group (preferably an alkanesulfonyl group having 1 to 32 carbon atoms,
For example, methanesulfonyl, octanesulfonyl), arenesulfonyl group (preferably an arenesulfonyl group having 6 to 32 carbon atoms, such as benzenesulfonyl, 1-naphthalenesulfonyl), and a sulfamoyl group (preferably a sulfamoyl group having 32 or less carbon atoms) Sulfamoyl, N, N-dipropylsulfamoyl, N-ethyl-N-dodecylsulfamoyl), sulfo group, phosphonyl group (preferably a phosphonyl group having 1 to 32 carbon atoms, for example, phenoxyphosphonyl, octyloxyphosphonyl) Phenylphosphonyl) or a phosphinoylamino group (preferably a phosphinoylamino group having 2 to 32 carbon atoms, for example, diethoxyphosphinoylamino, dioctyloxyphosphinoylamino group).

R ₂₁ is an alkyl group, an alkoxy group, a cyano group, an alkoxycarbonyl group, an amino group, an anilino group,
A carbonamido group and a sulfonamido group are preferable, and an alkyl group, an alkoxy group, an anilino group and a carbonamido group are more preferable.

[0057] R ₂₂ represents an alkyl group, an alkenyl group, an alkynyl group, an aryl group, a heterocyclic group, an alkoxycarbonyl group, an aryloxycarbonyl group or a carbamoyl group, preferably a carbon number and specific examples of these groups R ₂₁
And the same as the alkyl group, alkenyl group, alkynyl group, aryl group, heterocyclic group, alkoxycarbonyl group, aryloxycarbonyl group, and carbamoyl group described in the description of the group represented by. R ₂₂ is preferably an alkyl group, an alkoxycarbonyl group, and a carbamoyl group, more preferably an alkyl group having 1 to 8 carbon atoms, and most preferably a methyl group.

R ₂₃ represents a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group or a heterocyclic group;
The preferred carbon number and specific examples of these groups are the same as those of the alkyl group, alkenyl group, alkynyl group, aryl group and heterocyclic group described in the description of the group represented by R ₂₁ . R ₂₃
Is preferably an alkyl group or an aryl group.

The groups represented by R ₂₁ , R ₂₂ and R ₂₃ may further have a substituent, and preferred substituents are the groups represented by R ₁ .

Preferred specific examples of the compound represented by formula (SC-1) are shown below, but the invention is not limited thereto.

[0061]

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[0062]

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The compound represented by the general formula (SC-1) can be synthesized by the methods described in US Pat. No. 3,876,428, German Offenlegungsschrift 0LS2,428,431, and JP-A-62-7051.

Next, the compound represented by formula (SC-2) will be described in detail. R ₂₄ represents an alkyl group, an alkenyl group, an alkynyl group, an aryl group, a heterocyclic group, an alkoxy group, an aryloxy group, a heterocyclic oxy group, an amino group or an anilino group, and the preferred number of carbon atoms and specific examples of these groups are alkyl groups mentioned in the description of the groups represented by R _21, an alkenyl group, an alkynyl group, an aryl group, a heterocyclic group, an alkoxy group, an aryloxy group, the same as the heterocyclic oxy group, an amino group and an anilino group. R ₂₄ is preferably an alkyl group, an aryl group, a heterocyclic group, an alkoxy group, an aryloxy group, and an anilino group, and more preferably an alkyl group and an aryl group.

R ₂₅ represents an alkoxycarbonyl group, an aryloxycarbonyl group or a carbamoyl group. The preferred number of carbon atoms and specific examples of these groups are the alkoxycarbonyl group, aryloxycarbonyl group described in the description of the group represented by R _21. And the same as the carbamoyl group. R ₂₅
Is preferably an alkoxycarbonyl group and a carbamoyl group, and most preferably a carbamoyl group.

R ₂₆ represents an alkyl group, an alkenyl group, an alkynyl group, an aryl group or a heterocyclic group, and the preferred number of carbon atoms and specific examples of these groups are the alkyl groups mentioned in the description of the group represented by R ₂₁ ; The same as the alkenyl group, alkynyl group, aryl group, and heterocyclic group. R ₂₆ is preferably an alkyl group.

The groups represented by R ₂₄ , R ₂₅ and R ₂₆ may further have a substituent, and preferred substituents are the groups represented by R ₁ . R ₂₄ and R ₂₆ combine to form 5-7
A member ring may be formed.

Among the compounds represented by the general formula (SC-2), a compound represented by the following general formula (SC-3) or (SC-4) is preferable.

[0069]

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In the general formula (SC-3), R ₂₇ represents the general formula (SC-
Represents the same group as R ₂₅ in 2), R ₂₈ represents the same group as R ₂₁ in formula (SC-1), m represents an integer of 0-8. R ₂₇
Is preferably an alkoxycarbonyl group and a carbamoyl group, and most preferably a carbamoyl group. R ₂₈ is preferably a halogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, a heterocyclic group, an alkoxycarbonyl group, an aryloxycarbonyl group, or a carbamoyl group.
m is preferably from 0 to 2, and most preferably 0.

In the general formula (SC-4), R ₂₉ represents the general formula (SC-
Represents the same group as R ₂₅ in 2), R ₃₀ represents in the general formula (SC-1) the same groups as R _21, n is an integer of 0 to 6. R ₂₉
Is preferably an alkoxycarbonyl group and a carbamoyl group, and most preferably a carbamoyl group. R ₃₀ is preferably a halogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, a heterocyclic group, an alkoxycarbonyl group, an aryloxycarbonyl group, and a carbamoyl group.
n is preferably from 0 to 2, and most preferably 0.

Preferred specific examples of the compound represented by the formula (SC-2) are shown below, but the invention is not limited thereto.

[0073]

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[0074]

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[0075]

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[0076]

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[0077]

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The compound represented by the general formula (SC-2) can be synthesized by the method described in DE-A-196 29 142 A1.

The content of the compound represented by the general formula (SC-1) or (SC-2) is determined based on the total amount of the developing agent contained in the layer to which these are added and the layer adjacent to this layer. 5-100 mol%
Is preferred, and particularly preferably 10 to 60 mol%.

[C] Photosensitive layer (1) Photosensitive silver halide The silver halide usable in the light-sensitive material of the present invention includes silver iodobromide, silver bromide, silver chlorobromide, silver iodochloride, and silver chloride. Any of silver and silver iodochlorobromide may be used. The size of silver halide grains is
0.1 to 2 μm, especially 0.2 to 1.5 in terms of the diameter of a sphere of the same volume
μm is preferred. These can be used not only as the above-mentioned photosensitive silver halide grains but also as non-photosensitive silver halide grains without chemical sensitization.

The shape of the silver halide grains may be one having a normal crystal shape such as cubic, octahedral or tetradecahedral, or one having a hexagonal or rectangular tabular shape. Are tabular grains having an aspect ratio of 2 or more, preferably 8 to 50, and more preferably 20 or more, which is a value obtained by dividing by the thickness of the grains. Preferably 80%
It is preferable to use an emulsion which accounts for 90% or more of the above.

The thickness of these tabular grains is preferably
It is 0.3 μm or less, more preferably 0.2 μm or less, and most preferably 0.1 μm or less.

Also, US Pat. Nos. 5,494,789 and 5,503,970
No. 5,503,971, No. 5,536,632, etc., particles having a thickness smaller than 0.07 μm and having a higher aspect ratio can also be preferably used. Also U.S. Pat.
Nos. 400,463, 4,713,323, 5,217,858 and the like, and high silver chloride tabular grains having a (111) plane as a main plane and U.S. Pat.Nos. 5,264,337, 5,292,632, and 5,31
High silver chloride tabular grains having a (100) plane as a main plane described in US Pat. No. 0,635 or the like can also be preferably used. An example of actually using these silver halide grains is disclosed in Japanese Patent Application No. 8-46822.
Nos. 8-97344, 8-238672, and 9-41637.

The silver halide grains are preferably so-called monodisperse grains having a uniform grain size distribution. As a standard of monodispersity, the coefficient of variation obtained by dividing the standard deviation of the particle size distribution by the average particle size is preferably 25% or less, and more preferably 20% or less. It is also preferable that the halogen composition is uniform among the grains.

In the silver halide grains, the halogen composition in the grains may be made uniform, or sites having different halogen compositions may be intentionally introduced. Particularly, in order to obtain high sensitivity, grains having a laminated structure composed of a core (nucleus) and a shell (shell) having different halogen compositions are preferably used. It is also preferable to further grow grains after introducing a region having a different halogen composition to intentionally introduce dislocation lines. Further, it is also preferable that guest crystals having different halogen compositions are epitaxially bonded to the apexes and ridges of the formed host grains.

It is also preferable to dope polyvalent transition metal ions or polyvalent anions as impurities into silver halide grains. In particular, in the former, a halogeno complex using an iron group element as a central metal, a cyano complex, an organic ligand complex, and the like are preferable.

The amount of the photosensitive silver halide added was calculated in terms of silver.
0.05~15 g / m ^2, preferably from 0.1 to 8 g / m ^2.

(2) Preparation of Light-Sensitive Silver Halide Grains The method for preparing the silver halide grains of the present invention is well-known in the art, that is to say, "Physics and Chemistry of Photography" by Grafkid, published by Paul Monte (P. Glafkides). , Chimie et Phisique P
hotographique, Paul Montel, 1967), Photographic Emulsion Chemistry by Duffin, published by Focal Press (GF Duffin,
Photographic Emulsion Chemistry, Focal Press, 196
6), “Manufacture and coating of photographic emulsions” by Zelikuman et al., Focal Press (VLZelikman et al., Making and Coating)
Coating of Photographic Emulsion, Focal Press, 196
The method described in 4) etc. can be performed basically. That is, it can be prepared in various pH ranges such as an acidic method, a neutral method, and an ammonia method. As a method for supplying a water-soluble silver salt and a water-soluble halogen salt solution as a reaction solution, a one-side mixing method, a simultaneous mixing method, or the like can be used alone or in combination. Further, it is also preferable to use a controlled double jet method for controlling the addition of a reaction solution so as to keep pAg during the reaction at a target value. A method of keeping the pH value during the reaction constant is also used. For particle formation, the temperature of the system, pH or
Although a method of controlling the solubility of silver halide by changing the pAg value can be used, thioether, thioureas, rhodan salts and the like can be used as the solvent. Examples of these are described in JP-B-47-11386, JP-A-53-144319, and the like.

In preparing the silver halide grains of the present invention, a solution of a water-soluble silver salt such as silver nitrate and a solution of a water-soluble halide salt such as an alkali halide are usually controlled in an aqueous solution of a water-soluble binder such as gelatin. It is performed by supplying under conditions. After the formation of silver halide grains, it is preferable to remove excess water-soluble salts. For example, a gelatin solution containing silver halide particles is gelled, cut into strings, and washed with cold water to remove water-soluble salts, such as the Nudel washing method, inorganic salts comprising polyvalent anions (eg, sodium sulfate), anionic interface An activator, an anionic polymer (for example, sodium polystyrene sulfonate), or a gelatin derivative (for example, an aliphatic acylated gelatin, an aromatic acylated gelatin, an aromatic carbamoylated gelatin, etc.) is added to aggregate the gelatin to form an excess salt. May be used. When the sedimentation method is used, the removal of excess salts is quickly performed, which is preferable.

(3) Reducible Silver Salt The reducible silver salt that can be used in the present invention is relatively stable to light, but is exposed to a photocatalyst (such as a latent image of a photosensitive silver halide). ) And supplies silver ions when heated to 80 ° C. or higher in the presence of a reducing agent. As such a silver salt, the ligand is 4.0 to 10.0.
Complexes of organic or inorganic silver salts having a complex stability constant in the range of are preferred. Organic compounds that can be used to form organic silver salts include benzotriazoles, fatty acids and other compounds described in U.S. Pat. No. 4,500,626, columns 52-53. The acetylene silver described in U.S. Pat. No. 4,775,613 is also useful. Two or more organic silver salts may be used in combination. The organic silver salt can be used in an amount of 0.01 to 10 mol, preferably 0.01 to 1 mol, per 1 mol of the photosensitive silver halide. The total coating amount of light-sensitive silver halide emulsion and the organic silver salt, silver converted at 0.05 to 10 g / m ^2, and preferably from 0.1-4 g / m ^2. The silver donor can preferably comprise about 5 to 70% by weight of the photosensitive layer. Preferred organic silver salts include silver salts of organic compounds having a carboxyl group. Specific examples include silver salts of aliphatic carboxylic acids and silver salts of aromatic carboxylic acids, but are not limited thereto. Preferred examples of the silver salt of an aliphatic carboxylic acid include silver behenate, silver arachidate, silver stearate, silver oleate,
Examples thereof include silver laurate, silver caproate, silver myristate, silver palmitate, silver maleate, silver fumarate, silver tartrate, silver linoleate, silver butyrate and silver camphorate, and mixtures thereof. Also, a silver complex with a nitrogen acid described in JP-A-52-137321 can be preferably used. Specifically, 3-amino-1,2,4- described in JP-A-53-116144
Silver salts of triazoles and silver salts of substituted or unsubstituted benzotriazoles can be mentioned.

The organic silver preferably used in the present invention is the above-mentioned organic compound or its alkali metal salt (Na salt, K salt).
Salt, Li salt, etc.). A solution or suspension is prepared by reacting with silver nitrate. Regarding these preparation methods, the method described in Japanese Patent Application No. 11-104187 can be used.

In the present invention, it is preferable to use a method of preparing an organic silver salt by adding an aqueous solution of silver nitrate and an organic compound or an alkali metal salt solution thereof into a sealing means for mixing a liquid. More specifically,
The method described in 11-203413 can be used.

In the present invention, a water-soluble dispersant can be added to the aqueous solution of silver nitrate and the organic compound, or the alkali metal salt solution or reaction solution thereof during the preparation of the organic silver salt. Specific examples of the type and amount of the dispersant used here are described in JP-A-2000-305214.

The organic silver used in the present invention is preferably prepared in the presence of an alcohol. As alcohol, the third
Alcohols are preferred, compounds having a total carbon number of 15 or less are preferred, and compounds having a total carbon number of 10 or less are particularly preferred. Preferred examples of the tertiary alcohol include tert-butanol, but the tertiary alcohol that can be used in the present invention is not limited to this.

The tertiary alcohol used in the present invention may be added at any time during the preparation of organic silver, but it is preferable to dissolve the above-mentioned organic compound or its alkali metal salt before use. The amount of the alcohol used in the present invention is generally in the range of 0.01 to 10, preferably 0.03 to 1, in terms of mass ratio to water as a solvent at the time of preparing the silver salt of an organic acid.

The organic silver salt used in the present invention is preferably desalted. The desalting method is not particularly limited, and a known method can be used, but a known filtration method such as centrifugal filtration, suction filtration, ultrafiltration, and floc-forming water washing by a coagulation method can be preferably used. Regarding the method of ultrafiltration, the method described in Japanese Patent Application No. 11-115457 can be used.

In the present invention, in order to obtain an organic silver salt solid dispersion having a small particle size and no aggregation, an aqueous dispersion containing an organic silver salt as an image forming medium and substantially containing no photosensitive silver salt is used. It is preferable to use a dispersion method in which the liquid is converted into a high-speed flow and then the pressure is reduced. Regarding these dispersion methods, the method described in Japanese Patent Application No. 11-104187 can be used.

The shape and size of the organic silver salt which can be used in the present invention are not particularly limited.
A solid particulate dispersion of 0.05 μm to 10.0 μm is preferred. In the present invention, the size of the organic silver salt is represented by using a diameter (equivalent sphere diameter) when the shape of the silver salt particle observed by an electron microscope is approximated to a sphere. More preferred average particle size is 0.1 μm ~
5.0 μm, more preferably the average particle size is 0.1 μm to 2.0 μm.

The shape of the organic silver salt used in the present invention is not particularly limited, and may be needle-like, rod-like, plate-like, scale-like, or the like.

The organic silver salt solid fine particle dispersion used in the present invention preferably has a monodispersed particle size distribution. Specifically, the percentage (coefficient of variation) of the value obtained by dividing the standard deviation of the volume load average diameter by the volume load average diameter is 80% or less, more preferably 50% or less, and still more preferably 30% or less.

The organic silver salt solid fine particle dispersion used in the present invention comprises at least an organic silver salt and water. The ratio between the organic silver salt and water is not particularly limited, but the ratio of the organic silver salt to the whole is preferably 5 to 50% by mass, and particularly preferably 10 to 30% by mass. It is preferable to use the above-mentioned dispersing aid, but it is preferable to use the dispersing aid in a minimum amount within a range suitable for minimizing the particle size, and 0.5 to 30% by mass, especially 1 to 15% by mass based on the organic silver salt. Is preferable.

In the present invention, a metal ion selected from Ca, Mg, Zn and Ag may be added to the non-photosensitive organic silver salt. In the present invention, the addition amount of a metal ion selected from Ca, Mg, Zn and Ag is preferably 10 ⁻³ to 10 −10 per 1 mol of non-photosensitive organic silver.
^-1 mol is preferable, and particularly preferably 5 × 10 ^{−3 to} 5 × 10 ⁻² mol.

(4) Chemical sensitization and spectral sensitization The emulsion of the present invention is usually preferably subjected to chemical sensitization and spectral sensitization. As chemical sensitization, a chalcogen sensitization method using sulfur, selenium or tellurium compound, a noble metal sensitization method using gold, platinum, iridium, or the like, or a compound having an appropriate reducing property during grain formation, So-called reduction sensitization, in which high sensitivity is obtained by introducing a neutral silver nucleus, can be used alone or in various combinations.

As the spectral sensitization, cyanine dyes, merocyanine dyes, complex cyanine dyes, complex merocyanine dyes, holopolar dyes, hemicyanine dyes, which are adsorbed on silver halide grains to have sensitivity in the absorption wavelength range of the silver halide grains, are provided. A so-called spectral sensitizing dye such as a styryl dye or a hemioxonol dye is used alone or in combination, and is preferably used together with a supersensitizer.

(5) Additives The photosensitive silver halide and / or reducible silver salt in the present invention is further protected against the formation of additional fog by known antifoggants and stabilizer precursors. In addition, it is possible to stabilize against a decrease in sensitivity during storage of inventory. Suitable antifoggants, stabilizers and stabilizer precursors, which can be used alone or in combination, are described in U.S. Pat.
Nos. 2,131,038 and 2,694,716, thiazonium salts, U.S. Pat.Nos. 2,886,437 and 2,444,605 Azaindene, U.S. Pat.No. 2,728,663 Mercury salts, U.S. Pat. Sulfocatechol described in Patent 3,235,652, oxime, nitrone, nitroindazole described in British Patent No. 623,448, polyvalent metal salt described in U.S. Patent 2,839,405, thyuronium salt described in U.S. Patent 3,220,839,
And U.S. Pat.Nos. 2,566,263 and 2,597,915, palladium, platinum and gold salts, U.S. Pat.
Halogen-substituted organic compounds described in Nos. 5,442,202 and 4,442,202; U.S. Pat.Nos. 4,128,557 and 4,137,079;
There are triazines described in 4,138,365 and 4,459,350 and phosphorus compounds described in U.S. Pat. No. 4,411,985.

The addition of these antifoggants or stabilizers to the silver halide emulsion may be at any time during the preparation of the emulsion. After the completion of chemical sensitization, at the time of preparation of the coating solution, at the end of chemical sensitization, during chemical sensitization, before chemical sensitization, before desalting after completion of grain formation, during grain formation, or during addition before grain formation, etc. The methods can be used alone or in combination.

The addition amount of these antifoggants or stabilizers varies widely depending on the halogen composition and purpose of the silver halide emulsion, but generally ranges from 10 ^-6 to 10 ^-1 per mol of silver halide.
mol, preferably in the range of 10 ^-5 to 10 ^-2 mol.

The antifoggant preferably used in the present invention is an organic halide, for example, as described in JP-A-50-119624.
No. 54-58022, No. 56-70543, No. 56-99335, No. 61
No. -129642, No. 62-129845, JP-A-6-208191, No. 7-56
No. 21, No. 8-15809, U.S. Pat.No. 5,340,712, No. 5,36
No. 9,000 and 5,464,737. Among these, an organic polyhalogen compound represented by the following formula (II) is particularly preferred.

Q ^2- (Y) _n -CZ ¹ Z ² X (II)

In the formula (II), Q ² represents an optionally substituted alkyl group, aryl group or heterocyclic group.
Alkyl group represented by Q ² is a linear, branched or cyclic alkyl group, or a combination thereof, preferably having 1 to 20 carbon atoms, more preferably 1 to 12, more preferably 1 to
6. Preferably it is a tertiary alkyl group. The alkyl group represented by Q ² may have a substituent, for example, a halogen atom (fluorine atom, chlorine atom, bromine atom or iodine atom), alkyl group, alkenyl group, alkynyl group, aryl group, heterocyclic ring Groups (including N-substituted nitrogen-containing heterocyclic groups, such as morpholino groups), alkoxycarbonyl groups, aryloxycarbonyl groups, carbamoyl groups,
Imino group, imino group substituted by N atom, thiocarbonyl group, carbazoyl group, cyano group, thiocarbamoyl group,
An alkoxy group, an aryloxy group, a heterocyclic oxy group,
Acyloxy group, (alkoxy or aryloxy) carbonyloxy group, sulfonyloxy group, acylamide group, sulfonamide group, ureido group, thioureido group, imide group, (alkoxy or aryloxy) carbonylamino group, sulfamoylamino group, semicarbazide Group, thiosemicarbazide group, (alkyl or aryl) sulfonyluureide group, nitro group,
(Alkyl or aryl) sulfonyl group, sulfamoyl group, group containing phosphoric acid amide or phosphoric ester structure, silyl group, carboxyl group or salt thereof, sulfo group or salt thereof, phosphoric acid group, hydroxy group, quaternary ammonium group, etc. Is mentioned. These substituents may be further substituted with these substituents.

The aryl group represented by Q ² is a monocyclic or condensed-ring aryl group, preferably has 6 to 20 carbon atoms, more preferably has 6 to 16 carbon atoms, and still more preferably has 6 to 10 carbon atoms. A naphthyl group is preferred. The aryl group represented by Q ² may have a substituent, and the substituent may be any group as long as it does not adversely affect photographic performance. Examples include the same groups as the substituents.

The heterocyclic group represented by Q ² is a 5- to 7-membered saturated or unsaturated monocyclic or fused heterocyclic ring wherein the heterocyclic ring contains at least one heteroatom selected from the group consisting of nitrogen, oxygen and sulfur atoms. Those that are rings are preferred. Examples of heterocycles include:
Preferable examples include pyridine, quinoline, isoquinoline, pyrimidine, pyrazine, pyridazine, phthalazine, triazine, furan, thiophene, pyrrole, oxazole, benzoxazole, thiazole, benzothiazole, imidazole, benzimidazole, thiadiazole, and triazole. Pyridine,
They are quinoline, pyrimidine, thiadiazole and benzothiazole, particularly preferably pyridine, quinoline and pyrimidine. The heterocyclic group may have a substituent.

Q ² is preferably a phenyl group, a naphthyl group,
A quinolyl group, a pyridyl group, a pyrimidyl group, a thiadiazolyl group, and a benzothiazolyl group, and particularly preferably a phenyl group, a naphthyl group, a quinolyl group, a pyridyl group, and a pyrimidyl group.

The substituent for Q ² may have a ballast group used in photographic materials to reduce diffusivity, an adsorptive group to silver salts, or a group imparting water solubility, The polymers may be polymerized with each other to form a polymer, or the substituents may be bonded to each other to form a bis-type, tris-type, or tetrakis-type.

In the formula (II), Y represents a divalent linking group, preferably -SO _2- , -SO-, -CO-, and particularly preferably -SO _2- .

N represents 0 or 1, but is preferably 1.

Z ¹ and Z ² each independently represent a halogen atom (eg, fluorine, chlorine, bromine, iodine, etc.)
Most preferably, Z ¹ and Z ² are both bromine atoms.

X represents a hydrogen atom or an electron-withdrawing group. The electron-withdrawing group represented by X is a substituent whose Hammett's substituent constant σ _P can take a positive value, specifically, a cyano group, an alkoxycarbonyl group, an aryloxycarbonyl group, a carbamoyl group , A sulfamoyl group, an alkylsulfonyl group, an arylsulfonyl group, a halogen atom, an acyl group, a heterocyclic group and the like. X is preferably a hydrogen atom or a halogen atom, and most preferably a bromine atom.

As the organic polyhalogen compound represented by the formula (II), for example, US Pat. Nos. 3,874,946 and 4,756,9
No. 99, No. 5,340,712, No. 5,369,000, No. 5,464,
No. 737, JP-A-50-137126, JP-A-50-89020, JP-A-50-11962
No. 4, 59-57234, JP-A-7-2781, 7-5621, 9
-160164, 10-197988, 9-244177, 9-244178
Nos. 9-160167, 9-319022, 9-258367, 9-
265150, 9-319022, 10-197989, 11-242304
No., Japanese Patent Application No. 10-181459, No. 10-292864, No. 11-90095
And the compounds described in JP-A Nos. 11-89773 and 11-205330.

The organic polyhalogen compound represented by the formula (II) may be used alone or in combination of two or more. Usage, as the coating amount per photothermographic material 1 m ^2, 1 × 10
^-6 to 1 × 10 ^-2 mol / m ² , more preferably 1 × 1
0 ^{−5 to} 5 × 10 ⁻³ mol / m ² , more preferably 2 × 10 3
⁻⁵ to 1 × 10 ⁻³² mol / m ² .

The organic polyhalogen compound represented by the formula (II) may be added to any layer on the support as long as it is on the same surface as the photosensitive silver halide and the reducible silver salt. It is preferably added to a layer containing a reducible silver salt or a layer adjacent thereto.

The organic polyhalogen compound represented by the formula (II) can be used after being dissolved in water or a suitable organic solvent. Alternatively, an emulsified dispersion can be prepared and used according to an already well-known emulsification dispersion method. Alternatively, according to a well-known solid dispersion method, an organic polyhalogen compound powder can be dispersed in water and used. Preferred examples of the organic polyhalogen compound represented by the formula (II) are shown below, but the organic polyhalogen compound used in the present invention is not limited thereto.

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In the light-sensitive material of the present invention, the following general formula (F)
Compounds represented by any of -1) and (F-2) can be preferably used as an antifoggant. The general formula (F-
A water-insoluble metal salt of the compound represented by any of 1) and (F-2) can also be used. In this case, examples of the metal ion that forms a metal salt as a counter cation include Fe, Cu, Ag, and Hg. Above all
Is most preferred.

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In formula (F-1), R _f1 represents an alkyl group having 4 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or an aralkyl group having 7 to 20 carbon atoms. In Formula (F-2), R _f2 represents a hydrogen atom, an alkyl group having 4 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or an aralkyl group having 7 to 20 carbon atoms, and R _f3 has 4 carbon atoms.
Represents an alkyl group having 20 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or an aralkyl group having 7 to 20 carbon atoms. However, the total number of carbon atoms of R _f2 and R _f3 is 4 to 30.

C 4-20 represented by R _f1 , R _f2 or R _f3
The alkyl group may have a substituent described below, may be linear, branched or cyclic, and specific examples thereof include an n-butyl group and n -Hexyl group, n-octyl group, n-decyl group, n-dodecyl group, 2-ethylhexyl group, n-hexadecyl group, 6-methoxyhexyl group, 6-hydroxyhexyl group, and cyclohexyl group. The aryl group having 6 to 20 carbon atoms represented by R _f1 , R _f2 or R _f3 may have a substituent described below, and specific examples thereof include a phenyl group, a naphthyl group, and a 4-methoxyphenyl group. And the like. The aralkyl group having 7 to 20 carbon atoms represented by R _f1 , R _f2 or R _f3 may have a substituent described below, and specific examples thereof include a benzyl group, a phenethyl group, and a 4-chlorobenzyl group. And the like.

R _f1 is preferably an alkyl group having 6 to 12 carbon atoms or an aralkyl group having 7 to 12 carbon atoms, more preferably an alkyl group having 6 to 12 carbon atoms, particularly preferably 8 to 12 carbon atoms. Is a linear alkyl group. The general formula (F
-2), wherein R _f2 is a hydrogen atom, an alkyl group having 6 to 12 carbon atoms, an aryl group having 6 to 12 carbon atoms or an aralkyl group having 7 to 12 carbon atoms, and R _f3 is an alkyl having 6 to 12 carbon atoms. Group, carbon number 6
An aryl group or an aralkyl group having 7 to 12 carbon atoms, wherein the total number of carbon atoms of R _f2 and R _f3 is preferably 6 to 20, and R _f2 is an alkyl group having 6 to 12 carbon atoms. , Carbon number 6-1
An aryl group of 2 or an aralkyl group of 7 to 12 carbon atoms, wherein R _f3 is an aryl group of 6 to 12 carbon atoms or an aralkyl group of 7 to 1 carbon atoms.
2 is an aralkyl group, and the total number of carbon atoms of R _f2 and R _f3 is 6
Is more preferable, R _f2 is an alkyl group having 6 to 12 carbon atoms or an aryl group having 6 to 12 carbon atoms, and R _f3 is an aryl group having 6 to 12 carbon atoms or 7 to 12 carbon atoms. It is an aralkyl group, and it is particularly preferable that the total number of carbon atoms of R _f2 and R _f3 is 6 to 14.

In the general formulas (F-1) and (F-2), M ₂ represents a hydrogen atom or a cation. Examples of the cation include alkali metal ions (sodium ion, potassium ion, etc.), alkaline earth metal ions (magnesium ion, calcium ion, barium ion, etc.), ammonium ions (unsubstituted ammonium ion, tetramethylammonium ion, etc.), Fe Ions, Cu ions, Ag ions, Hg ions and the like. M is preferably a hydrogen atom. Also M ₂
Are Fe ions, Cu ions, Ag ions, Hg ions, etc.
It is also preferable that the compound represented by any one of the general formulas (F-1) and (F-2) is a poorly water-soluble metal salt. In this case, M ₂ is particularly preferably a Ag ions.

As described above, R _f1 , R _f2 and R _f3 may have a substituent. Preferred examples of the substituent include:
A halogen atom, an alkyl group (including a cycloalkyl group and a bicycloalkyl group), an alkenyl group (including a cycloalkenyl group and a bicycloalkenyl group), an alkynyl group,
Aralkyl group, aryl group, heterocyclic group, cyano group, hydroxyl group, nitro group, carboxyl group, alkoxy group, aryloxy group, silyloxy group, heterocyclic oxy group, acyloxy group, carbamoyloxy group, alkoxycarbonyloxy group, aryl Oxycarbonyloxy group, amino group (including anilino group), acylamino group, aminocarbonylamino group, alkoxycarbonylamino group, aryloxycarbonylamino group, sulfamoylamino group, alkyl and arylsulfonylamino group, mercapto group, alkylthio Group, arylthio group, heterocyclic thio group, sulfamoyl group, sulfo group, alkyl and arylsulfinyl group, alkyl and arylsulfonyl group, acyl group, aryloxycarbonyl group, alkoxy Carbonyl group, a carbamoyl group, an aryl or heterocyclic azo group, an imido group, a phosphino group, phosphinyl group, phosphinyloxy group, phosphinylamino group, a silyl group.

The substituent is more specifically a halogen atom (eg, a chlorine atom, a bromine atom, an iodine atom), an alkyl group [a linear, branched, or cyclic substituted or unsubstituted alkyl group. An alkyl group (preferably an alkyl group having 1 to 10 carbon atoms such as methyl, ethyl, n-propyl, isopropyl, t-butyl, n-octyl, 2-chloroethyl,
Cyanoethyl, 2-ethylhexyl), cycloalkyl group (preferably substituted or unsubstituted cycloalkyl group having 3 to 10 carbon atoms, for example, cyclohexyl, cyclopentyl), alkenyl group [linear, branched, cyclic substituted or unsubstituted Represents an alkenyl group. An alkenyl group (preferably a substituted or unsubstituted alkenyl group having 2 to 10 carbon atoms,
For example, vinyl, allyl), a cycloalkenyl group (preferably a substituted or unsubstituted cycloalkenyl group having 3 to 10 carbon atoms, ie, a monovalent group obtained by removing one hydrogen atom from a cycloalkene having 3 to 10 carbon atoms) For example, 2-cyclopenten-1-yl, 2-cyclohexen-1-yl), a heterocyclic group (preferably a 5- or 6-membered substituted or unsubstituted aromatic or non-aromatic heterocyclic compound) A monovalent group obtained by removing one hydrogen atom, more preferably a 5- or 6-membered aromatic heterocyclic group having 3 to 10 carbon atoms, for example, 2-furyl, 2-thienyl,
2-pyrimidinyl, 2-benzothiazolyl), cyano group, hydroxyl group, nitro group, carboxyl group, alkoxy group (preferably substituted or unsubstituted alkoxy group having 1 to 10 carbon atoms, for example, methoxy, ethoxy, isopropoxy, t-butoxy, n-octyloxy, 2-methoxyethoxy), aryloxy group (preferably having 6 carbon atoms)
To 10 substituted or unsubstituted aryloxy groups such as phenoxy, 2-methylphenoxy, 4-t-butylphenoxy, 3-nitrophenoxy), silyloxy groups (preferably silyloxy groups having 3 to 10 carbon atoms, for example, , Trimethylsilyloxy, t-butyldimethylsilyloxy), a heterocyclic oxy group (preferably having 2 to 10 carbon atoms)
A substituted or unsubstituted heterocyclic oxy group, 1-phenyltetrazol-5-oxy, 2-tetrahydropyranyloxy), an acyloxy group (preferably a formyloxy group,
A substituted or unsubstituted alkylcarbonyloxy group having 2 to 10 carbon atoms, a substituted or unsubstituted arylcarbonyloxy group having 6 to 10 carbon atoms, for example, formyloxy, acetyloxy, pivaloyloxy, benzoyloxy, p-methoxyphenylcarbonyl Oxy), a carbamoyloxy group (preferably a substituted or unsubstituted carbamoyloxy group having 1 to 10 carbon atoms, for example, N, N-dimethylcarbamoyloxy, N, N-diethylcarbamoyloxy, morpholinocarbonyloxy), alkoxycarbonyl An oxy group (preferably a substituted or unsubstituted alkoxycarbonyloxy group having 2 to 10 carbon atoms, such as methoxycarbonyloxy, ethoxycarbonyloxy, t-butoxycarbonyloxy, n-octylcarbonyloxy), aryloxyca A rubonyloxy group (preferably a substituted or unsubstituted aryloxycarbonyloxy group having 7 to 10 carbon atoms, for example, phenoxycarbonyloxy, p-methoxyphenoxycarbonyloxy), an amino group (preferably an amino group, a From
10 substituted or unsubstituted alkylamino groups, 6 carbon atoms
To 10 substituted or unsubstituted anilino groups, for example, amino, methylamino, dimethylamino, anilino, N-methyl-anilino), acylamino group (preferably formylamino group, substituted or unsubstituted having 1 to 10 carbon atoms) An alkylcarbonylamino group, a substituted or unsubstituted arylcarbonylamino group having 6 to 10 carbon atoms, for example,
Formylamino, acetylamino, pivaloylamino,
Benzoylamino), aminocarbonylamino group (preferably substituted or unsubstituted aminocarbonylamino having 1 to 10 carbon atoms such as carbamoylamino, N, N-
Dimethylaminocarbonylamino, N, N-diethylaminocarbonylamino, morpholinocarbonylamino), alkoxycarbonylamino group (preferably having 2 carbon atoms)
10 substituted or unsubstituted alkoxycarbonylamino groups, for example, methoxycarbonylamino, ethoxycarbonylamino, t-butoxycarbonylamino, n-octadecyloxycarbonylamino, N-methyl-methoxycarbonylamino), aryloxycarbonylamino group (preferably Is a substituted or unsubstituted aryloxycarbonylamino group having 7 to 10 carbon atoms such as phenoxycarbonylamino, p-chlorophenoxycarbonylamino), a sulfamoylamino group (preferably substituted or unsubstituted having 0 to 10 carbon atoms or Unsubstituted sulfamoylamino groups, for example, sulfamoylamino, N, N-dimethylaminosulfonylamino, Nn-octylaminosulfonylamino), alkyl and arylsulfonylamino groups (preferably having 1 to 10 carbon atoms) Or unsubstituted alkylsulfonylamino, substituted or unsubstituted arylsulfonylamino having 6 to 10 carbon atoms, such as methylsulfonylamino, butylsulfonylamino, phenylsulfonylamino, 2,3,5-trichlorophenylsulfonylamino, p- Methylphenylsulfonylamino), mercapto group, alkylthio group (preferably substituted or unsubstituted alkylthio group having 1 to 10 carbon atoms, for example, methylthio, ethylthio), arylthio group (preferably substituted or unsubstituted having 6 to 10 carbon atoms) Arylthio, for example, phenylthio, p-chlorophenylthio, m-methoxyphenylthio), a heterocyclic thio group (preferably having 2 carbon atoms)
To 10 substituted or unsubstituted heterocyclic thio groups, for example, 2-
Benzothiazolylthio, 1-phenyltetrazol-5-ylthio), sulfamoyl group (preferably having 0 to
10 substituted or unsubstituted sulfamoyl groups, for example,
N-ethylsulfamoyl, N- (3-dodecyloxypropyl) sulfamoyl, N, N-dimethylsulfamoyl, N-
Acetylsulfamoyl, N-benzoylsulfamoyl, N- (N'-phenylcarbamoyl) sulfamoyl),
Sulfo group, alkyl and arylsulfinyl group (preferably substituted or unsubstituted alkylsulfinyl group having 1 to 10 carbon atoms, substituted or unsubstituted arylsulfinyl group having 6 to 10 carbon atoms, for example, methylsulfinyl, ethylsulfinyl, phenylsulfinyl) , P-methylphenylsulfinyl), alkyl and arylsulfonyl groups (preferably substituted or unsubstituted alkylsulfonyl groups having 1 to 10 carbon atoms, substituted or unsubstituted arylsulfonyl groups having 6 to 10 carbon atoms, for example, methylsulfonyl, Ethylsulfonyl, phenylsulfonyl, p-methylphenylsulfonyl), acyl group (preferably formyl group, carbon number 2)
To 10 substituted or unsubstituted alkylcarbonyl groups, substituted or unsubstituted arylcarbonyl groups having 7 to 10 carbon atoms such as acetyl, pivaloyl, 2-chloroacetyl, benzoyl), and aryloxycarbonyl groups (preferably A substituted or unsubstituted aryloxycarbonyl group having the number of 7 to 10, for example, phenoxycarbonyl, o-chlorophenoxycarbonyl, m-nitrophenoxycarbonyl), an alkoxycarbonyl group (preferably a substituted or unsubstituted having 2 to 10 carbon atoms) Alkoxycarbonyl group, for example, methoxycarbonyl, ethoxycarbonyl, t-butoxycarbonyl), carbamoyl group (preferably substituted or unsubstituted carbamoyl having 1 to 10 carbon atoms, for example, carbamoyl, N-methylcarbamoyl, N, N- Dimethylcarbamoy , N- (methylsulfonyl) carbamoyl), aryl and heterocyclic azo groups (preferably substituted or unsubstituted arylazo groups having 6 to 10 carbon atoms, substituted or unsubstituted heterocyclic azo groups having 3 to 10 carbon atoms, for example, Phenylazo, p-chlorophenylazo, 5-ethylthio-1,3,4-thiadiazol-2-ylazo), imide group (preferably N-succinimide, N-
Phthalimide), phosphino group (preferably having 2 carbon atoms)
To 12 substituted or unsubstituted phosphino groups, for example,
Dimethylphosphino, diphenylphosphino, methylphenoxyphosphino), phosphinyl group (preferably,
A substituted or unsubstituted phosphinyl group having 2 to 12 carbon atoms, for example, phosphinyl, diethoxyphosphinyl), a phosphinyloxy group (preferably a substituted or unsubstituted phosphinyloxy group having 2 to 12 carbon atoms) For example, diphenoxyphosphinyloxy), a phosphinylamino group (preferably a substituted or unsubstituted phosphinylamino group having 2 to 10 carbon atoms, for example, dimethoxyphosphinylamino, dimethylaminophosphinyl) Amino), a silyl group (preferably a substituted or unsubstituted silyl group having 3 to 10 carbon atoms, for example, trimethylsilyl,
t-butyldimethylsilyl, phenyldimethylsilyl).

The compound represented by any of formulas (F-1) and (F-2) can be synthesized by a known method. Below, the general formula
Specific examples of the compound represented by either (F-1) or (F-2) are shown below, but the present invention is not limited thereto.

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Various known methods can be used for incorporating the compound represented by any of formulas (F-1) and (F-2) into the photothermographic material of the present invention. For example, these compounds are dissolved in a suitable solvent (such as methanol, ethanol or ethyl acetate), or an alkali metal is formed by replacing the hydrogen of the mercapto group of the compound with sodium ions or potassium ions, and forming an alkali metal solution. It can be added to the coating solution in the state described above. The addition of such a solution may be at any stage of the coating solution preparation,
The method can be appropriately selected from a method of adding the silver halide emulsion to the silver halide emulsion in advance, a method of adding the silver halide emulsion to other components, and a method of adding the silver halide emulsion in the final step of preparing a coating solution. Further, a fine crystal of a silver salt of a compound represented by any of the general formulas (F-1) and (F-2) is prepared and dispersed in water or a gelatin solution,
The obtained dispersion can be added to the coating solution. For such a silver salt, a known technique can be used as a method for preparing silver halide, and a method described in JP-A-1-100177 can also be used.

The amount of the compound represented by any one of formulas (F-1) and (F-2) can be adjusted in a wide range in order to obtain the desired performance. 1
You may add 1 * 10 < ^-5 > -1 mol per mol. The amount of addition, when the compounds represented by one of general formula (F-1) and (F-2) is not in the form of a salt, or M ₂ is an alkali metal cation, a silver halide The order of 10 ^-4 to 10 ^-2 mol per mol of emulsion is represented by the general formula (F-1) and
When the compound represented by any of (F-2) is a silver salt, it is preferably on the order of 10 ^-2 to 1 mol.

The photographic additives used in the light-sensitive material of the present invention as described above are described in Research Disclosure (hereinafter abbreviated as RD) No. 17643 (December 1978), N.
o. 18716 (November 1979) and No. 307105 (November 1989)
Month). The relevant locations are shown below.

[0142]

[D] Coupler The photothermographic material of the present invention has a coupler compound on the same surface of the support as the photosensitive silver halide and the reducible silver salt. The coupler reacts with the reducing agent released from the compound of formula (I) or with its own oxidant to form a dye.

The coupler compound used in the present invention is a compound known as a coupler known in the photographic industry, and a 2-equivalent or 4-equivalent coupler is used. Examples of photographic couplers include “Conventional Organic Compounds for Color Photography” by Nobuo Furudate (Journal of the Society of Synthetic Organic Chemistry, Vol. 41, 439).
P. 1983).
Research Disclosure 37038 (February 1995) 80
The couplers described in detail on pages 85-87 and 87-89 can be used.

More specifically, examples of yellow image forming couplers include pivaloylacetamide type, benzoylacetamide type, malon diester type, malon diamide type, dibenzoyl methane type, benzothiazolyl acetamide type, malon ester monoamide type, and the like. Benzoxazolylacetamide type, benzimidazolylacetamide type, benzothiazolylacetamide type, cycloalkylcarbonylacetamide type, indoline-2-ylacetamide type, quinazolin-4-one-2-ylacetamide described in U.S. Pat.No. 5,021,332 Type, benzo-1,2,4-thiadiazine-1,1-dioxide-3 described in 5,021,330
-Ilacetamide type, couplers described in EP 421221A, couplers described in U.S. Pat.No. 5,455,149, couplers described in EP 0622673 and described in EP 0953871, 0953872, 0953873. And 3-indoloylacetamide type couplers. Methine dye releasing couplers described in U.S. Pat. Nos. 5,447,819 and 5,457,004, and JP-A-2000-206655 are also preferable as the yellow coupler used in the present invention.

Examples of magenta color image forming couplers include 5-pyrazolone type, 1H-pyrazolo [1,5-a] benzimidazole type and 1H-pyrazolo [5,1-C] [1,2,4] triazole type , 1H-pyrazolo [1,5-B] [1,2,4] triazole type, 1H-imidazo [1,2-B] pyrazole type, cyanoacetophenone type, active propene type described in WO93 / 01523, WO93 / 075
34, the enamine type, 1H-imidazo [1,2-B] [1,2,
4] Triazole type couplers and US Pat. No. 4,871,652
And the couplers described in the above item.

The cyan image forming couplers include, for example, phenol type, naphthol type and European Patent Publication 0294453.
2,5-diphenylimidazole type, 1H-pyrrolo [1,2-B] [1,2,4] triazole type, 1H-pyrrolo [2,1-C]
[1,2,4] triazole type, JP-A-4-188137, 4-19034
No. 7, pyrrole type, JP-A-1-315736, 3-hydroxypyridine type described in U.S. Pat.No. 5,164,289
The pyrrolopyrazole type described in No. 4, the pyrroloimidazole type described in JP-A-4-174429, U.S. Pat.
No. 585, pyrazolopyrimidine type, JP-A-4-204
No. 730, pyrrolotriazine type couplers described in U.S. Pat.No.4,746,602, U.S. Pat.
The couplers described in JP-A-04,783, the couplers described in JP-A-5,162,196, and the couplers described in EP 0556700 are exemplified.

Specific examples of representative coupler compounds that can be used in the present invention are shown below, but the present invention is not limited by these specific examples.

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CP-115 (compound Inv-16 described in JP-A-2000-206655)

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The coupler compound used in the present invention can be easily synthesized by a method known in the photographic art described in the above patents and the like relating to couplers.

The coupler compound used in the present invention may be water or a suitable organic solvent such as alcohols (methanol, ethanol, propanol, fluorinated alcohol), ketones (acetone, methyl ethyl ketone), dimethylformamide, dimethyl sulfoxide, methyl cellosolve, etc. Can be dissolved and used.

The present invention relates to EP-A-101690.
It is also preferable to add a heterocyclic compound having a ClogP sufficient to improve sensitivity described in No. 2. One example (compound X) of this heterocyclic compound is shown below. Further, a triazole compound having a ClogP value of 4.75 to 9.0 described in JP-A-2001-051383, a purine compound having a ClogP value of 2 or more and less than 7.2 described in JP-A-2001-051384, JP-A-2001-051385
No. 1 or more and less than 7.6 Mercapto-1,2,4
It is also preferable to add a thiadiazole or mercapto-1,2,4-oxadiazole compound or a tetrazole compound having a ClogP value of 2 or more and less than 7.8 described in JP-A-2001-051386. These compounds may be added to the photosensitive material as fine oil droplets dissolved in a high-boiling organic solvent as in the case of other oil-soluble compounds such as a developing agent and a coupler used in the present invention, or a solvent miscible with water. And may be added to the binder. Further, silver salts of these compounds may be prepared in advance and added to the light-sensitive material. In that case, in addition to the above-described methods, they may be added to the light-sensitive material as a solid dispersion. The addition amount of these compounds can be adjusted in a wide range to obtain the desired performance, but is generally on the order of 1 × 10 ^-5 to 1 mol per mol of the silver halide emulsion. When the compound of the present invention is used in a free form or as an alkali metal salt, a preferable addition amount is based on silver halide.
In the order of 10 ^-3 to 10 ^-1 mol, when used as a silver salt
It is on the order of 10 ^-2 to 1 mol.

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Embedded image Compound X

These couplers and hydrophobic additives such as a color developing agent can be introduced into a layer of a light-sensitive material by a known method such as the method described in US Pat. No. 2,322,027. In this case, U.S. Patent Nos. 4,555,470 and 4,53
6,466, 4,536,467, 4,587,206, 4,555,476
No. 4,599,296, JP-B-3-62256, and the like, a high-boiling organic solvent can be used in combination with a low-boiling organic solvent having a boiling point of 50 to 160 ° C., if necessary. These dye-donating couplers, high-boiling organic solvents and the like can be used in combination of two or more.

The amount of the high boiling organic solvent is 10 g or less, preferably 5 g or less, more preferably 1 g to 0.1 g per 1 g of the hydrophobic additive used. Further, the amount is preferably 1 ml or less, more preferably 0.5 ml or less, particularly preferably 0.3 ml or less, based on 1 g of the binder.

A dispersion method using a polymer described in JP-B-51-39853 and JP-A-51-59943, or a method of adding a fine particle dispersion described in JP-A-62-3024 or the like Can also be used. In the case of a compound which is substantially insoluble in water, it can be dispersed and contained as fine particles in a binder in addition to the above method.

In dispersing the hydrophobic compound in the hydrophilic colloid, various surfactants can be used. For example, the surfactants described in JP-A-59-157636 and the aforementioned Research Disclosure can be used. Japanese Patent Application Nos. 5-204325 and 6-19247, West German Patent No. 1,932,2
The phosphate ester type surfactants described in 99A can also be used.

According to a well-known solid dispersion method, the powder of the coupler compound can be dispersed in water by a ball mill, a colloid mill, a sand grinder mill, a Menton-Gaulin, a microfluidizer, or ultrasonic waves. .

The coupler compound used in the present invention may be added to any layer on the support as long as it is on the same surface as the photosensitive silver halide and the reducible silver salt. Alternatively, it is preferably added to a layer adjacent thereto.

The amount of the coupler compound used in the present invention is preferably from 0.2 to 200 mmol, more preferably from 0.3 to 100 mmol, even more preferably from 0.5 to 30 mmol per 1 mol of silver.
mmol. Even if only one kind of coupler compound is used, 2
More than one species may be used in combination.

When the compound of the present invention is used in a photographic material, the amount of the coupler that can be used in the present invention is 0.2 to 10 mmol per 1 mol of silver, preferably 0.5 to 10 mmol.
１1 mmol.

In the present invention, the following functional couplers may be used.

(A) As couplers in which the color-forming dye has an appropriate diffusivity, US Pat. No. 4,366,237, GB 2,125,570, EP 96,87
3B, couplers described in DE 3,234,533.

(B) As a coupler for correcting unnecessary absorption of a coloring dye, a yellow colored cyan coupler described in EP 456,257A1, a yellow colored magenta coupler described in the EP, and a magenta described in US Pat. No. 4,833,069 Colored cyan coupler, US4,837,136 (2), WO9
Colorless masking couplers of formula (A) of claim 1 of 2/11575 (especially the exemplified compounds on pages 36 to 45).

(C) Compounds (including couplers) which react with oxidized developing agents to release photographically useful compound residues
Examples thereof include the following (i) to (vi). (i) Development inhibitor releasing compound: Formula described in EP378,236A1
Compounds represented by formulas (I) to (IV), compounds represented by formula (I) described in EP436,938A2, compounds represented by formula (1) of EP568,037A, and compounds represented by formula (I) described in EP440,195A2 ), (II) and (III). (ii) Bleaching accelerator releasing compound: Formula (I) of EP 310,125A2,
Compound represented by (I ') and claim 1 of JP-A-6-59411
A compound represented by the formula (I): (iii) Ligand releasing compound: a compound represented by LIG-X described in claim 1 of US Pat. No. 4,555,478. (iv) Leuco dye releasing compound: column 3, US 4,749,641
Compounds 1 to 6; fluorescent dye releasing compounds, US 4,774,18
The compound represented by COUP-DYE of Claim 1 of Claim 1. (v) Development accelerator or fog release compounds: US 4,656,
Compounds represented by formulas (1), (2) and (3) in column 3 of 123 and ExZK-2 described in EP 450,637A2. (vi) Compound that releases a group that becomes a dye only after leaving:
Compounds represented by the formula (I) in claim 1 of US Pat. No. 4,857,447, compounds represented by the formula (1) in Japanese Patent Application No. 4-134523, EP4
Compounds represented by the formulas (I), (II), and (III) described in JP-A-40,195A2; compounds represented by the formula (I) in claim 1 of Japanese Patent Application No. 4-325564; A compound represented by LIG-X according to claim 1 of the item (1).

Such a functional coupler is used in an amount of 0.05 to 10 mol based on 1 mol of the coupler contributing to color development described above.
Preferably, 0.1 to 5 mol is used.

[E] Precursor In general, a base is required for processing a photographic light-sensitive material, but a base is not necessarily required for the light-sensitive material of the present invention. However, a base may be used for the purpose of accelerating the development, accelerating the reaction between the compound of the general formula (I) described below and the coupler, and accelerating the color development of the formed dye. In the light-sensitive material of the present invention, various base supply methods can be adopted. For example, when a base generating function is imparted to the photosensitive material side, it can be introduced into the photosensitive material as a base precursor. Examples of such a base precursor include salts of an organic acid and a base which are decarboxylated by heat, compounds which release amines by an intramolecular nucleophilic substitution reaction, Rossen rearrangement or Beckmann rearrangement. This example is described in U.S. Pat. Nos. 4,514,493 and 4,657,848.

The light-sensitive material of the present invention may contain a nucleophile or a nucleophile precursor for the purpose of accelerating the reaction between the compound of the formula (I) and the coupler. Various nucleophile precursors are known, but it is convenient to release a nucleophile during thermal development by using a precursor of a type that generates (or releases) a base by heating. A typical example of a base precursor that generates a base by heating is a pyrolytic (decarboxylation) base precursor composed of a salt of a carboxylic acid and a base. When the decarboxylation type base precursor is heated, the carboxyl group of the carboxylic acid undergoes a decarboxylation reaction to release the base. As the carboxylic acid, sulfonylacetic acid or propiolic acid, which is easily decarboxylated, is used. It is preferable that the sulfonylacetic acid and the propiolic acid have, as a substituent, an aromatic group (aryl group or unsaturated heterocyclic group) that promotes decarboxylation. The base precursor of sulfonyl acetate is described in JP-A-59-168441, and the base precursor of propiolate is described in JP-A-59-180537. The base component of the decarboxylation type base precursor is preferably an organic base, and more preferably amidine, guanidine or a derivative thereof. The organic base is preferably a diacid, triacid or tetraacid, more preferably a diacid, and most preferably an amidine derivative or a guanidine derivative.

The diacid, triacid or tetraacid precursor of the amidine derivative is described in JP-B-7-59545. For a precursor of a diacid, triacid or tetraacid base of a guanidine derivative, see JP-B-8-1032.
There is a description in No.1. The diacid base of the amidine derivative or guanidine derivative is (A) a divalent group that binds two amidine moieties or guanidine moieties, (B) a substituent of the amidine moieties or guanidine moieties, and (C) two amidine moieties or guanidine moieties. Consists of a linking group. Examples of the substituent (B) include an alkyl group (including a cycloalkyl group), an alkenyl group,
Includes alkynyl groups, aralkyl groups and heterocyclic residues. Two or more substituents may combine to form a nitrogen-containing heterocyclic ring. The connecting group of (C) is preferably an alkylene group or a phenylene group. Hereinafter, examples of the diacid base precursor of the amidine derivative or the guanidine derivative will be described.

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[F] Hot Solvent In the present invention, it is preferable to include a hot solvent. Here, the term "thermal solvent" means a solid at ambient temperature, but shows a mixed melting point together with other components at the heat treatment temperature used or lower, and liquefies during thermal development to become Or an organic material having an action of promoting thermal transfer of a dye. As the thermal solvent, a compound that can be a solvent for a developing agent, a compound having a high dielectric constant that promotes physical development of a silver salt, a compound that is compatible with a binder and acts to swell the binder, and the like are useful.

Examples of the thermal solvent which can be used in the present invention include, for example, US Pat. Nos. 3,347,675, 3,667,959,
3,438,776, 3,666,477, Research Disclosure No. 17,643, JP-A-51-19525, 53-24829
No. 53-60223, No. 58-118640, No. 58-198038, No.
59-229556, 59-68730, 59-84236, 60-1912
No. 51, No. 60-232547, No. 60-14241, No. 61-52643,
62-78554, 62-42153, 62-44737, 63-535
No. 48, No. 63-161446, JP-A No. 1-224751, No. 2-863,
Compounds described in JP-A-2-120739, JP-A-2-123354, JP-A-4-289856 and the like can be mentioned. Specifically, urea derivatives (urea, dimethylurea, phenylurea, etc.), amide derivatives (eg, acetamido, stearylamide, p-toluamide, p-propanoyloxyethoxybenzamide, etc.),
Sulfonamide derivatives (eg, p-toluenesulfonamide) and polyhydric alcohols (eg, 1,6-hexanediol, pentaerythritol, D sorbitol, polyethylene glycol, etc.) are preferred. Hereinafter, specific examples of typical thermal solvents that can be used in the present invention will be described.

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[G] Binder In the photothermographic material of the present invention, a binder is used for a non-photosensitive layer such as a photosensitive layer, a colored layer, a protective layer, and an intermediate layer. As the binder, well-known natural or synthetic resins such as gelatin, polyvinyl acetal, polyvinyl chloride, polyvinyl acetate, cellulose acetate,
Any one can be selected from polyolefin, polyester, polystyrene, polyacrylonitrile, polycarbonate, SBR latex purified by ultrafiltration (UF), and the like. Of course, copolymers and terpolymers are also included. If necessary, these polymers can be used in combination of two or more kinds. Such a polymer is used in an amount sufficient to hold the components therein. That is, it is used in a range effective to function as a binder. The effective range can be appropriately determined by those skilled in the art.

The binder of the light-sensitive material is preferably hydrophilic, and examples thereof include those disclosed in the above-mentioned Research Disclosure and JP-A-64-13546. Among them, gelatin and gelatin and other water-soluble binders, such as polyvinyl alcohol,
Combinations with modified polyvinyl alcohol, cellulose derivatives, acrylamide polymers and the like are preferred. The appropriate coating amount of the binder is 1 to 25 g / m ² , preferably 3 to 20 g / m ² , and more preferably 5 to 15 g / m ² . Among them, gelatin is used at a ratio of 50% to 100%, preferably 70% to 100%.

[H] Support As a support for the photosensitive material, "Basics of Photographic Engineering-Silver salt photography" edited by The Photographic Society of Japan, published by Corona Co., Ltd. (Showa 54) 22
Photographic supports described on pages 3-240 are preferred. Specifically, polyethylene terephthalate, polyethylene naphthalate, polycarbonate, syndiotactic polystyrene, celluloses (for example, triacetyl cellulose)
And the like.

These supports may be subjected to heat treatment (crystallinity and orientation control), uniaxial and biaxial stretching (orientation control), blending of various polymers, surface treatment, etc., in order to improve optical and physical properties. It can be carried out.

As a support, for example, JP-A-4-1246
No. 45, No. 5-40321, No. 6-35092 and No. 6-31875 are preferably used to record photographic information and the like using the support having a magnetic recording layer.

On the back surface of the support of the photosensitive material, see JP-A-8-29
It is also preferred to apply a water-resistant polymer as described in 2514.

A polyester support particularly preferably used for the light-sensitive material having the magnetic recording layer is disclosed in Published Technical Report
94-6023 (Invention Association; March 15, 1994). The thickness of the support is 5 to 200 μm, preferably 40 to 120
μm.

[II] Layer structure of photothermographic material The photothermographic material of the present invention is preferably composed of three or more photosensitive layers having different color sensitivity. Each light-sensitive layer contains at least one silver halide emulsion layer, and typically comprises a plurality of silver halide emulsion layers having substantially the same color sensitivity but different sensitivities. At this time, it is preferable to use grains having a larger so-called aspect ratio obtained by dividing the grain projected diameter by the grain thickness, as the silver halide grains have a larger grain projected diameter. The photosensitive layer is a unit photosensitive layer having color sensitivity to any of blue light, green light and red light,
In a multilayer silver halide color photographic light-sensitive material, generally, the arrangement of the unit light-sensitive layers is, in order from the support side, a red-sensitive layer,
A green color sensitive layer and a blue color sensitive layer are provided in this order. However, the order of installation may be reversed depending on the purpose, or the order of installation may be such that different photosensitive layers are sandwiched between layers having the same color sensitivity. The total thickness of the photosensitive layer is generally 2 to 40 µm, preferably 5 to 25 µm.

In the present invention, as a colored layer using an oil-soluble dye which can be decolorized by treatment, a yellow filter layer,
A magenta filter layer and an antihalation layer can be used. Accordingly, for example, when the photosensitive layer is provided in the order of a red photosensitive layer, a green photosensitive layer, and a blue photosensitive layer from the side closest to the support, a yellow filter layer and a green photosensitive layer are provided between the blue photosensitive layer and the green photosensitive layer. A magenta filter layer can be provided between the red photosensitive layer and the red photosensitive layer, and a cyan filter layer (antihalation layer) can be provided between the red photosensitive layer and the support. These colored layers may be in direct contact with the emulsion layer or may be arranged so as to be in contact with an intermediate layer such as gelatin. The amount of the dye used is set such that the transmission density of each layer is 0.03 to 3.0, more preferably 0.1 to 1.0, for blue, green and red light, respectively. In particular,
Although it depends on ε and the molecular weight of the dye, 0.005 to 2.0 mmol / m ² may be used, and more preferably 0.05 to 1.0 mmol / m ² .

As described in DE 1,121,470 or GB 923,045, a plurality of silver halide emulsion layers constituting each unit light-sensitive layer are formed by directing two layers of a high-speed emulsion layer and a low-speed emulsion layer toward a support. It is preferable to arrange them so that the sensitivities become lower sequentially. JP-A-57-112751, 62-200350, 6
As described in JP-A-2-206541 and JP-A-62-206543, a low-sensitivity emulsion layer may be provided on the side remote from the support, and a high-sensitivity emulsion layer may be provided on the side close to the support.

As a specific example, from the side farthest from the support,
Low-sensitive blue photosensitive layer (BL) / High-sensitive blue photosensitive layer (BH) / High-sensitive green photosensitive layer (GH) / Low-sensitive green photosensitive layer (GL) / High-sensitive red photosensitive layer (RH) /
In order of low sensitivity red photosensitive layer (RL), or BH / BL / GL / GH / RH / RL
Or in the order of BH / BL / GH / GL / RL / RH.

As described in JP-B-55-34932, the blue-sensitive layer / GH / RH / GL is selected from the side farthest from the support.
/ RL can be arranged in this order. JP-A-56-2573
8, as described in JP-A-62-63936, the layers can be arranged in the order of blue-sensitive layer / GL / RL / GH / RH from the side farthest from the support.

As described in JP-B-49-15495, the upper layer is a silver halide emulsion layer having the highest sensitivity, the middle layer is a silver halide emulsion layer having a lower sensitivity, and the lower layer is a layer having a higher sensitivity than the middle layer. An example is an arrangement in which a silver halide emulsion layer having a low sensitivity is arranged and three layers having different sensitivities are sequentially reduced in sensitivity toward a support. Even when such a three-layer structure having different photosensitivity is used,
As described in JP-A-59-202464, in the same color-sensitive layer, a medium-speed emulsion layer / a high-speed emulsion layer / a low-speed emulsion layer may be arranged in this order from the side away from the support.

In addition, high-speed emulsion layers / low-speed emulsion layers / medium-speed emulsion layers, or low-speed emulsion layers / medium-speed emulsion layers / high-speed emulsion layers may be arranged in this order. Also, in the case of four or more layers, the arrangement may be changed as described above.

To improve color reproducibility, US Pat. No. 4,663,27
1, 4,705,744, 4,707,436, JP-A-62-160448,
It is preferable to arrange a donor layer (CL) having a multilayer effect having a spectral sensitivity distribution different from that of the main photosensitive layers such as BL, GL, and RL described in JP-A-63-89850 adjacent to or near the main photosensitive layer.

In the present invention, the dye-providing coupler and the color developing agent (or a precursor thereof) may be contained in the photosensitive layer, but if they can react, they may be separately added to another layer. Can also. For example, when the layer containing the color developing agent and the layer containing silver halide are formed as separate layers, the raw storability of the light-sensitive material can be improved.

The relationship between the spectral sensitivity of each layer and the hue of the coupler is arbitrary. If a cyan coupler is used for the red photosensitive layer, a magenta coupler is used for the green photosensitive layer, and a yellow coupler is used for the blue photosensitive layer, it can be directly applied to conventional color paper. Projection exposure is possible.

The photothermographic material of the present invention may contain a protective layer, an undercoat layer, an intermediate layer, a yellow filter layer, an antihalation layer, etc. between the photosensitive layers and on the uppermost layer and the lowermost layer, in addition to the photosensitive layer and the support. May be provided, and various auxiliary layers such as a back layer may be provided on the side opposite to the support. These include the aforementioned couplers, developing agents and DI
An R compound, a color mixing inhibitor, a dye, and the like may be contained.
Specifically, the layer constitution as described in the above patent, U.S. Pat.
Undercoat layer as described in 5,051,335, JP-A-1-67838
No., an intermediate layer having a solid pigment as described in JP-A-61-20943, JP-A-1-120553, JP-A-5-34884, a reducing agent and a DIR compound as described in JP-A-2-64634. Having an intermediate layer, U.S. Pat.Nos. 5,017,454 and 5,139,919, JP-A-2-35044
Intermediate layer having an electron transfer agent as described in
It is possible to provide a protective layer having a reducing agent as described in JP-A-249245 or a layer obtained by combining them.

Dyes which can be used in the yellow filter layer and the antihalation layer are preferably those which are decolored or removed at the time of development and do not contribute to the density after processing.

When the dye in the yellow filter layer and the antihalation layer is decolored or removed at the time of development, the amount of the dye remaining after processing is 1/3 or less, preferably 1/1, immediately before coating.
0 or less.

The light-sensitive material of the present invention may be used by mixing two or more dyes in one colored layer. For example, three kinds of dyes of yellow, magenta and cyan can be mixed and used in the above-mentioned antihalation layer.

Specific examples include the dyes described in European Patent Application EP549,489A and the dyes ExF2 to Ex6 described in JP-A-7-152129. Dyes dispersed in a solid as described in Japanese Patent Application No. 6-259805 can also be used.

Further, the mordant and the binder may be dyed with a mordant. In this case, as the mordant and dye, those known in the field of photography can be used, and US Pat. No. 4,500,62
No. 6, JP-A-61-88256, JP-A-62-244043, JP-A-62-24403
The mordants described in No. 6, etc. can be used.

A decolorizable leuco dye or the like can be used. Specifically, a leuco dye which has been colored in advance with a developer of a metal salt of an organic acid disclosed in JP-A-1-150132 can be used. it can. The leuco dye and the developer complex are decolorized by reacting with heat or an alkali agent.

Known leuco dyes can be used, and Moriga and Yoshida, “Dyes and Chemicals”, p. 9, p.
"New Edition Dye Handbook", p. 242 (Maruzen, 1970), R. Garner "Re
"Ports on the Progress of Appl. Chem." 56, p. 199 (1971), "Dyes and Chemicals" 19, p. 230 (Chemical Products Industry Association, 1974), "Colorants" 62, p. 288 (1989), "Dyeing" Industry ", 32, 208 and the like.

As a color developer, a metal salt of an organic acid is preferably used in addition to an acid clay-based color developer, a phenol formaldehyde resin. As metal salts of organic acids, metal salts of salicylic acids, metal salts of phenol-salicylic acid-formaldehyde resin, rhodan salts, metal salts of xanthogenates and the like are useful, and zinc is particularly preferable as the metal.
Among the above developers, oil-soluble zinc salicylate salts described in U.S. Pat. Nos. 3,864,146 and 4,046,941 and JP-B-52-1327 can be used.

An oil-soluble dye which decolorizes during processing in the presence of a decoloring agent can also be used. As the dye to be used, cyclic ketomethylene compounds described in Japanese Patent Application No. 8-329124 (eg, 2-pyrazolin-5-one, 1,2,3,6-tetrahydropyridine-2,6-dione, rhodanin, hydantoin,
Thiohydantoin, 2,4-oxazolidinedione, isoxazolone, barbituric acid, thiobarbituric acid, indandione, dioxopyrazolopyridine, hydroxypyridine, pyrazolidinedione, 2,5-dihydrofuran-2
-One, pyrrolin-2-one) or a methylene group sandwiched by electron-withdrawing groups (eg, -CN, -SO ₂ R ₁ , -COR ₁ , -COO
R ₁ , -CON (R ₂ ) ₂ , -SO ₂ N (R ₂ ) ₂ , -C [= C (CN) ₂ ] R ₁ , -C [= C (C
N) ₂ ] N (R ₁ ) ₂ (R ₁ represents an alkyl group, an alkenyl group, an aryl group, a cycloalkyl group, or a heterocyclic group, and R ₂ represents a hydrogen atom or a group described in R ₁ ) Nucleus consisting of a compound having a methylene group), a basic nucleus (for example, pyridine, quinoline, indolenine, oxazole,
Imidazole, thiazole, benzoxazole, benzimidazole, benzothiazole, oxazoline, naphthoxazole, pyrrole, aryl group (for example, phenyl group, naphthyl group) and heterocyclic group (for example, pyrrole, indole, furan, thiophene, imidazole,
Pyrazole, indolizine, quinoline, carbazole,
Phenothiazine, phenoxazine, indoline, thiazole, pyridine, pyridazine, thiadiazine, pyran,
Thiopyran, oxadiazole, benzoquinoline, thiadiazole, pyrrolothiazole, pyrrolopyridazine, tetrazole, oxazole, coumarin, chroman) and a compound having a methine group, or (NC) ₂ C
= C (CN) -R ₃ (R ₃ is an aryl group or a heterocyclic group) is preferable.

The above-described decolorizable dye is used in a state where oil droplets dissolved in oil and / or an oil-soluble polymer are dispersed in a hydrophilic binder. An emulsification dispersion method is preferable as the preparation method, and for example, a method described in US Pat. No. 2,322,027 can be used. In this case, U.S. Patent 4,555,470
Nos. 4,536,466, 4,587,206, 4,555,476,
High boiling oils such as those described in JP-B-4,599,296 and JP-B-3-62256 can be used in combination with a low-boiling organic solvent having a boiling point of 50 ° C to 160 ° C, if necessary. Two or more high boiling oils can be used in combination. Oil-soluble polymers can be used in place of or in combination with oils, examples of which are described in WO 88/00723. The amount of high boiling oil and / or polymer depends on 1 g of dye used
0.01 g to 10 g, preferably 0.1 g to 5 g.

As a method of dissolving the dye in the polymer, a latex dispersion method can be used. Specific examples of the step and the latex for impregnation are described in US Pat. No. 4,199,36.
No. 3, West German Patent Application (OLS) No. 2,541,274, No. 2,541,230
And Japanese Patent Publication No. 53-41091 and European Patent Publication No. 029104.

When dispersing the oil droplets in the hydrophilic binder, various surfactants can be used. For example, Japanese Unexamined Patent Publication No. 59-157636, No. 5 of the prior art (March 22, 1991,
Surfactants described on pages 136 to 138 (Aztec Co., Ltd.) can be used. Japanese Patent Application No. 5-204325, 6-
The phosphate ester type surfactants described in No. 19247 and West German Patent No. 932,299A can also be used.

As the hydrophilic binder, a water-soluble polymer is preferable. Examples include gelatin, proteins of gelatin derivatives, or cellulose derivatives, starch, gum arabic,
Examples include natural compounds such as polysaccharides such as dextran and pullulan, and synthetic polymer compounds such as polyvinyl alcohol, polyvinylpyrrolidone, and acrylamide polymer.
These water-soluble polymers can be used in combination of two or more. Particularly preferred is a combination with gelatin.
Gelatin may be selected from lime-processed gelatin, acid-processed gelatin, and so-called demineralized gelatin having a reduced content of calcium and the like according to various purposes, and may be used in combination.

The above-mentioned oil-soluble dyes are decolorized during processing in the presence of a decoloring agent. Decoloring agents include alcohols or phenols, amines or anilines, sulfinic acids or salts thereof, sulfites or salts thereof, thiosulfates or salts thereof, carboxylic acids or salts thereof, hydrazines, guanidines, aminoguanidines, amidines , Thiols, cyclic or chain active methylene compounds, cyclic or chain active methine compounds, and anionic species generated from these compounds.

Of these, hydroxyamines, sulfinic acids, sulfurous acid, guanidines, aminoguanidines, heterocyclic thiols, cyclic or linear active methylene, and active methine compounds are particularly preferred. Are guanidines and aminoguanidines.

It is considered that the above-mentioned decolorizing agent comes into contact with the dye during the treatment and decolorizes the dye by nucleophilic addition to the dye molecule. Preferably, the film surfaces of the dye-containing silver halide light-sensitive material are superposed and heated after imagewise exposure or simultaneously with imagewise exposure in the presence of water and a processing member containing a decolorant or decolorant precursor. Thereafter, by peeling both off, a color-developed image is obtained on the silver halide light-sensitive material and the dye is decolorized. In this case, the concentration of the dye after decoloring is 1/3 or less, preferably 1/5 or less of the original concentration. The amount of the decoloring agent used is 0.1 to 200 times, preferably 0.5 to 100 times, the mole of the dye.

At temperatures lower than the decolorization start temperature (T ° C.), the dye is colored, but at a temperature higher than T, at least a part of the dye is decolorized, and a reversible decolorable dye whose change is reversible is used. Alternatively, a method may be used in which the temperature at the time of reading is set to be equal to or higher than the decoloring temperature (T ° C.) to prevent the deterioration of S / N at the time of reading due to the concentration of the dye. Such a reversible dye can be prepared using a combination of a leuco dye, a phenolic developer and a higher alcohol described in JP-B-51-44706.

For the light-sensitive material, a hardener, a surfactant, a photographic stabilizer, an antistatic agent, a slipping agent, a matting agent,
Latex, formalin scavengers, dyes, UV absorbers and the like can be used. Specific examples thereof are described in the above-mentioned Research Disclosure and Japanese Patent Application No. 8-30103. Examples of particularly preferred antistatic agents are
_{ZnO, TiO 2, SnO 2,} AL 2 O 3, In 2 O 3, SiO 2, MgO, BaO, MoO
₃ , metal oxide fine particles such as V ₂ O ₅ .

[III] Image Forming Method The photothermographic material of the present invention may be developed by any method, but is usually developed by elevating the temperature of the photosensitive material exposed imagewise. A preferred embodiment of the heat developing machine used is a type in which the photothermographic material is brought into contact with a heat source such as a heat roller or a heat drum.
No., Patent No. 684453, JP-A-9-292695, JP-A-9-2973
No. 85 and WO95 / 30934, as a non-contact type thermal developing machine, JP-A-7-13294, International Publication WO97 / 28489
Nos. 97/28488 and 97/28487. A particularly preferred embodiment is a non-contact type thermal developing machine. The preferred development temperature is 80 to 250 ° C, more preferably 100 to 140 ° C. The development time is 1
The time is preferably 180 seconds, more preferably 10 to 90 seconds.

FIG. 1 shows an example of the configuration of a heat developing machine used in the heat developing process of the photothermographic material of the present invention. FIG. 1 is a side sectional view of the heat developing machine. The heat developing machine shown in FIG. 1 carries the heat developing photosensitive material 10 into a heating unit while correcting and preheating the heat developing photosensitive material 10 into a flat shape (the lower roller is a heat roller) and the heat developing photosensitive material 10 after the heat development. It has a pair of unloading rollers 12 that unloads from the heating unit while correcting the shape.
The photothermographic material 10 is moved from the carry-in roller pair 11 to the carry-out roller pair 12
Developed while transported to In the transporting means for transporting the photothermographic material 10 during the thermal development, a plurality of rollers 13 are provided on the side in contact with the surface having the photosensitive layer, and the non-woven fabric (for example, aromatic A smooth surface 14 to which a group polyamide or Teflon (registered trademark) is attached. The back surface of the photothermographic material 10 is conveyed by sliding over the smooth surface 14 by driving a plurality of rollers 13 that come into contact with the surface having the photosensitive layer. The heating means is provided on the upper portion of the roller 13 and the lower portion of the smooth surface
A heater 15 is provided so that the heater 10 is heated from both sides. As a heating means in this case, a plate heater or the like can be used. The clearance between the roller 13 and the smooth surface 14 varies depending on the member of the smooth surface, but is appropriately adjusted to a clearance that allows the photothermographic material 10 to be conveyed. Preferably it is 0 to 1 mm.

The material of the surface of the roller 13 and the member of the smooth surface 14 may be any material as long as it has high-temperature durability and does not hinder the conveyance of the photothermographic material 10. The member is preferably a nonwoven fabric made of aromatic polyamide or Teflon (PTFE). It is preferable to use a plurality of heaters as the heating means and to set the heating temperature freely.

The heating section is composed of a preliminary heating section A having a carry-in roller pair 11 and a heat development processing section B provided with a heater 15. The preliminary heating section A upstream of the heat development processing section B is provided. Is
It is desirable to set the temperature and time lower than the heat development temperature (for example, about 10 to 30 ° C.) and sufficient for evaporating the amount of water in the heat development photosensitive material 10.
It is preferable that the temperature is set higher than the glass transition temperature (Tg) of the support so that development unevenness does not occur.

A guide plate 16 is provided downstream of the heat development processing section B, and a slow cooling section having the carry-out roller pair 12 and the guide plate 16
C is installed. The guide plate 16 is preferably made of a material having low thermal conductivity, and is preferably cooled gradually.

Although the illustrated example has been described above, the thermal developing machine used in the present invention is not limited to this.
Various configurations such as those described in No. 4 may be used. In the case of a multi-stage heating method which is preferably used in the present invention, two or more heat sources having different heating temperatures may be provided so that heating is continuously performed at different temperatures.

In the present invention, after forming a color image by thermal development, the remaining silver halide and / or developed silver may or may not be removed. As a method of outputting to another material based on the image information, ordinary projection exposure may be used, or the image information may be photoelectrically read by measuring the density of transmitted light, and output using the signal.
The material to be output need not be a photosensitive material, and may be, for example, a sublimation type thermosensitive recording material, an ink jet material, an electrophotographic material, a full color direct thermosensitive recording material, or the like. An example of a preferred embodiment of the present invention is that after forming a color image by thermal development, the image information is transmitted by using a diffused light and a CCD image sensor without performing an additional process of removing the remaining silver halide and developed silver. Read photoelectrically by density measurement,
After conversion into a digital signal, image processing is performed, and the image is output by a heat development color printer, for example, a pictography 3000 of Fuji Photo Film Co., Ltd. In this case, a good print can be obtained quickly without using any processing liquid used in conventional color photography. In this case, since the digital signal can be arbitrarily processed and edited, the captured image can be freely corrected, deformed, processed, and output.

In the present invention, another bleach-fixing step for further removing the silver halide and the developed silver remaining in the light-sensitive material after the development is not essential. However, a fixing step and / or a bleaching step may be provided in order to reduce the load of reading image information and to enhance image storability. In that case, normal liquid treatment may be used, but Japanese Patent Application No. Hei 8-8997
It is preferable to carry out a heat treatment step together with another sheet coated with a treatment agent as described in No. 7. The heating temperature in this case is preferably 50 ° C. as in the developing step, and particularly preferably set to the same temperature as in the developing step.

In the present invention, after an image is obtained on a photosensitive material, a color image is obtained on another recording material based on the information. As the method, image information is read photoelectrically by measuring the density of transmitted light, converted into a digital signal, and after image processing, is output to another recording material by the signal. The output materials are, in addition to photosensitive materials using silver halide,
Sublimation type thermosensitive recording materials, full color direct thermosensitive recording materials, ink jet materials, electrophotographic materials and the like may be used.

[0236]

EXAMPLES The present invention will be described in more detail with reference to the following Examples, but it should not be construed that the invention is limited thereto.

Example 1 {Preparation of Highly Sensitive Silver Halide Emulsion} 930 ml of distilled water containing 0.37 g of gelatin having an average molecular weight of 15,000, 0.37 g of oxidized gelatin and 0.7 g of potassium bromide was placed in a reaction vessel.
The temperature was raised to ° C. Silver nitrate 0.34 with vigorous stirring
30 ml of an aqueous solution containing 0.2 g of potassium bromide and 30 ml of an aqueous solution containing 0.24 g of potassium bromide were added over 20 seconds. 1 minute at 40 ° C after addition
, The temperature of the reaction solution was raised to 75 ° C. 27.0 g of gelatin whose amino group was modified with trimellitic acid was distilled water 2
After adding with 00 ml, an aqueous solution containing 23.36 g of silver nitrate 100
ml and 80 ml of an aqueous solution containing 16.37 g of potassium bromide were added over a period of 36 minutes while increasing the addition flow rate. Then, 250 ml of an aqueous solution containing 83.2 g of silver nitrate and an aqueous solution containing potassium iodide at a molar ratio of 3:97 to potassium bromide (potassium bromide concentration: 26%) were added while the flow rate was accelerated, and the silver in the reaction solution was increased. It was added for 60 minutes so that the potential was -50 mV with respect to the saturated calomel electrode. Further aqueous solution containing 18.7 g of silver nitrate
75 ml of a 21.9% aqueous solution of potassium bromide over 10 minutes, and the silver potential of the reaction
It was added to be 0 mV. After maintaining the temperature at 75 ° C. for 1 minute after the completion of the addition, the temperature of the reaction solution was lowered to 40 ° C. Then p-
Sodium iodide acetamidobenzenesulfonate monohydrate
100 ml of an aqueous solution containing 10.5 g was added, and the pH of the reaction solution was adjusted to 9.0.
Was prepared. Next, 50 ml of an aqueous solution containing 4.3 g of sodium sulfite was added. After completion of the addition, the temperature was maintained at 40 ° C. for 3 minutes, and then the temperature of the reaction solution was raised to 55 ° C. Adjust the pH of the reaction solution to 5.8
After the preparation, sodium benzenethiosulfinate was added to 0.1%.
8 mg, potassium hexachloroiridate (IV) 0.04 mg
After adding 5.5 g of potassium bromide and keeping at 55 ° C. for 1 minute, 180 ml of an aqueous solution containing 44.3 g of silver nitrate and 160 ml of an aqueous solution containing 34.0 g of potassium bromide and 8.9 mg of potassium hexacyanoferrate (II) were added. Added over 30 minutes. The temperature was lowered and desalting was performed according to a standard method. After completion of desalting, gelatin was added so as to be 7% by weight, and the pH was adjusted to 6.2.

The obtained emulsion contained hexagonal tabular grains having an average grain diameter of 1.15 μm, an average grain thickness of 0.12 μm, and an average aspect ratio of 24.0 expressed in terms of sphere-equivalent diameter. This emulsion was designated as emulsion A-1.

The number of nuclei formed was changed by making the amounts of silver nitrate and potassium bromide added in the early stage of the grain formation different from those of the emulsion A-1, and the average grain size expressed by a diameter equivalent to a sphere was 0.75. Emulsion A-2 consisting of hexagonal tabular grains having an average grain thickness of 0.11 μm and an average aspect ratio of 14.0, and an average grain diameter of 0.52 μm represented by a sphere-equivalent diameter, an average grain thickness of 0.09 μm, and an average aspect Emulsions A-3 each comprising hexagonal tabular grains having a ratio of 11.3 were prepared. However, potassium hexachloroiridate (IV) and iron hexacyano
The amount of potassium (II) acid added was inversely proportional to the particle volume, and the amount of sodium p-iodoacetamidobenzenesulfonate monohydrate added was proportional to the perimeter of the particles.

After adding 5.6 ml of a 1% aqueous solution of potassium iodide to Emulsion A-1 at 40 ° C., the following spectral sensitizing dye was added to 8.2 × 1
0 ^-4 mol / mol Ag, Compound I, potassium thiocyanate, chloroauric acid, sodium thiosulfate and mono (pentafluorophenyl) diphenylphosphine selenide were added for spectral and chemical sensitization. After chemical sensitization, stabilizer
S was added. At this time, the amount of the chemical sensitizer was adjusted so that the degree of chemical sensitization of the emulsion was optimized.

[0241]

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The blue-sensitive emulsion thus prepared was designated as A-1b. Similarly, each emulsion was subjected to spectral sensitization and chemical sensitization to prepare emulsions A-2b and A-3b. However, the addition amount of the spectral sensitizing dye was changed according to the surface area of the silver halide grains in each emulsion. The amount of each chemical used for chemical sensitization was also adjusted so that the degree of chemical sensitization of each emulsion was optimized.

Similarly, by changing the spectral sensitizing dye, green-sensitive emulsions A-1g, A-2g and A-3g, red-sensitive emulsions A-1r, A-2r and
A-3r was prepared.

[0244]

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[0245]

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<Preparation of silver salt of scaly fatty acid> 87.6 g of behenic acid (product name: Edenor C22-85R) manufactured by Henkel, distilled water 42
3 ml, 49.2 ml of 5N-NaOH aqueous solution, and tert-butanol 120
The mixture was stirred at 75 ° C. for 1 hour and reacted to obtain a sodium behenate solution. Separately, an aqueous solution of 40.4 g of silver nitrate 20
6.2 ml (pH 4.0) was prepared and kept at 10 ° C. 635 ml
Reaction vessel containing distilled water and 30 ml of tert-butanol
While maintaining the temperature at 30 ° C., while stirring, the entire amount of the sodium behenate solution and the entire amount of the silver nitrate aqueous solution were added at a constant flow rate of 62%.
Minutes were added over 10 seconds and 60 minutes. At this time, only the aqueous silver nitrate solution was added for 7 minutes and 20 seconds after the start of the aqueous silver nitrate solution, and then the addition of the sodium behenate solution was started. After the addition of the aqueous silver nitrate solution was completed, only the sodium behenate solution was added for 9 minutes and 30 seconds. Was added. At this time,
The temperature inside the reaction vessel was set at 30 ° C., and the external temperature was controlled so that the liquid temperature became constant. The piping of the addition system of the sodium behenate solution was kept warm by steam tracing, and the steam opening was adjusted so that the liquid temperature at the outlet at the tip of the addition nozzle became 75 ° C. The piping of the silver nitrate aqueous solution addition system was kept warm by circulating cold water outside the double pipe. The addition position of the sodium behenate solution and the addition position of the aqueous silver nitrate solution were arranged symmetrically about the stirring axis, and were adjusted to a height such that they did not come into contact with the reaction solution.

After the completion of the addition of the sodium behenate solution, the mixture was left to stir at the same temperature for 20 minutes, and the temperature was lowered to 25 ° C. Thereafter, the solid content was separated by suction filtration, and the solid content was washed with water until the conductivity of the filtered water became 30 μS / cm. Thus, a fatty acid silver salt was obtained. The obtained solid content was stored as a wet cake without drying.

The morphology of the obtained silver behenate particles was evaluated by electron microscopic photographing. The average values were a = 0.14 μm and b =
The crystal had a size of 0.4 μm, c = 0.6 μm, an average aspect ratio of 5.2, an average equivalent sphere diameter of 0.52 μm, and a variation coefficient of equivalent sphere diameter of 15%.
In addition, the length of each side when the particles were approximated to a rectangular parallelepiped was set to a, b, and c from the shorter side.

To a wet cake having a dry solid content of 100 g, 7.4 g of polyvinyl alcohol (trade name: PVA-217)
And water were added to make the total amount 385 g, and the mixture was pre-dispersed with a homomixer.

Next, the pre-dispersed stock solution was subjected to a pressure of 17 with a dispersing machine (trade name: Microfluidizer M-110S-EH, manufactured by Microfluidics International Corporation, using a G10Z interaction chamber).
The mixture was adjusted to 50 kg / cm ² and treated three times to obtain a silver behenate dispersion. The cooling operation was set at a dispersion temperature of 18 ° C. by installing coiled heat exchangers before and after the interaction chamber, respectively, and adjusting the temperature of the refrigerant.

<Method for Preparing Silver 5-Amino-3-benzylthiotriazole> 5-Amino-3-benzylthiotriazole 1
1.3 g, sodium hydroxide 1.1 g, gelatin 10 g in water 1000
The mixture was dissolved in L, kept at 50 ° C, adjusted to pH 2.8-3.2 with 1N nitric acid, and stirred. Next, 8.5 g of silver nitrate was dissolved in 100 ml of water, and the solution was added to the above solution over 2 minutes. The emulsion was allowed to settle by adjusting the pH of the emulsion to remove excess salt. Thereafter, the pH was adjusted to 6.0, and a yield of 400 g of 5-amino-3
-A silver benzylthiotriazole emulsion was obtained.

<Method of preparing silver 5-butylbenzotriazole> 9.6 g of 5-butylbenzotriazole, 1.1 g of sodium hydroxide, and 10 g of gelatin were dissolved in 1000 L of water, and the mixture was stirred at 50 ° C. and stirred. Next, 4.25 g of silver nitrate was dissolved in 50 ml of water, and the solution was added to the above solution over 2 minutes. Then 1N NaOH
After adding 27 ml and stirring for 5 minutes, 4.25 g of silver nitrate was dissolved in 50 ml of water, and the solution was added to the above solution over 2 minutes. Of this emulsion
The emulsion was sedimented by adjusting the pH to remove excess salt. Thereafter, the pH was adjusted to 6.0 to obtain a 400 g yield of silver 5-butylbenzotriazole emulsion.

<Preparation of a 10% by mass dispersion of a mercapto compound> 5 kg of 1-phenyl-2-heptyl-5-mercapto-1,3,4-triazole was added to a modified polyvinyl alcohol (Kuraray).
5 kg of a 20% by weight aqueous solution of Poval MP-203 manufactured by
And 3 kg to give a slurry. The slurry was sent by a diaphragm pump and dispersed by a horizontal sand mill (UVM-2: manufactured by Imex Co., Ltd.) filled with zirconia beads having an average diameter of 0.5 mm for 6 hours, and then water was added to reduce the concentration of the mercapto compound to 10%. It adjusted so that it might be the mass%, and the mercapto dispersion was obtained. The mercapto compound particles contained in the thus obtained mercapto compound dispersion have a median diameter of
0.40 μm and the maximum particle size was 2.0 μm or less. This mercapto compound dispersion was filtered with a polypropylene filter having a pore size of 10.0 μm to remove foreign substances such as dust. Immediately before use, the mixture was again filtered through a polypropylene filter having a pore size of 10 μm.

<Preparation of 20% by mass dispersion of organic polyhalogen compound-1> 5 kg of tribromomethylnaphthyl sulfone
And modified polyvinyl alcohol (Poval manufactured by Kuraray Co., Ltd.)
2.5 kg of a 20% aqueous solution of MP203) and 213 of a 20% aqueous solution of sodium triisopropylnaphthalenesulfonate.
g and 10 kg of water were mixed well to form a slurry. This slurry is fed by a diaphragm pump and has an average diameter of 0.5 mm.
Horizontal sand mill filled with zirconia beads (UVM-2:
The mixture was dispersed for 5 hours with IMEX Co., Ltd.). Thereafter, 0.2 g of benzoisothiazolinone sodium salt and water were added to adjust the concentration of the organic polyhalogen compound to 20% by mass to obtain an organic polyhalogen compound dispersion. The organic polyhalogen compound particles contained in the polyhalogen compound dispersion thus obtained had a median diameter of 0.36 μm and a maximum particle diameter of 2.0 μm or less. This organic polyhalogen compound dispersion was filtered with a polypropylene filter having a pore size of 3.0 μm to remove foreign substances such as dust.

<Preparation of 25% by mass dispersion of organic polyhalogen compound-2> 5 kg of tribromomethylnaphthyl sulfone
Was prepared in the same manner as in Dispersion-1 except that 5 kg of tribromomethyl (4- (2,4,6-trimethylphenylsulfonyl) phenyl) sulfone was used in place of the above. %, And filtered. The organic polyhalogen compound particles contained in the organic polyhalogen compound dispersion thus obtained have a median diameter of 0.38 μm.
m, and the maximum particle size was 2.0 μm or less. The organic polyhalogen compound dispersion was passed through a polypropylene filter having a pore size of 3.0 μm to remove foreign substances such as dust.

<Preparation of 30% by mass dispersion of organic polyhalogen compound-3> 5 kg of tribromomethylnaphthyl sulfone
Was prepared in the same manner as in Dispersion-1, except that 5 kg of tribromomethylphenylsulfone was used instead of 5 kg of an aqueous solution of MP203 of 20% by mass, and the organic polyhalogen compound was adjusted to 30% by mass. And then filtered. The organic polyhalogen compound particles contained in the organic polyhalogen compound dispersion thus obtained have a median diameter of 0.
41 μm and the maximum particle size was 2.0 μm or less. This organic polyhalogen compound dispersion was filtered with a polypropylene filter having a pore size of 3.0 μm to remove foreign substances such as dust.
It was stored at 10 ° C or less until use.

<Preparation of 5% by mass solution of phthalazine compound> 8 kg of modified polyvinyl alcohol MP203 manufactured by Kuraray Co., Ltd.
Was dissolved in 174.57 kg of water, and then 3.15 kg of a 20% by mass aqueous solution of sodium triisopropylnaphthalenesulfonate.
And a 70% by mass aqueous solution of 6-isopropylphthalazine 14.28
kg was added to prepare a 5% by mass aqueous solution of 6-isopropylphthalazine.

<Solid Fine Particle Dispersion of Base Precursor>
Preparation of (a)> 64 g of base precursor compound BP-41, 28
g of diphenyl sulfone and 10 g of surfactant Demol N (manufactured by Kao Corporation) were mixed with 220 ml of distilled water, and the mixture was subjected to a sand mill (1/4 Gallon Sand Grinder Mill, manufactured by Imex Co., Ltd.). Dispersion of solid particles of a base precursor compound having an average particle diameter of 0.2 μm
(a) was obtained.

<Preparation of Dye Solid Fine Particle Dispersion> 9.6 g of cyanine dye compound and 5.8 g of sodium P-dodecylbenzenesulfonate were mixed with 305 ml of distilled water, and the resulting mixture was sand-milled (1/4 Gallon sand grinder). mill,
The beads were dispersed using IMEX Co., Ltd.) to obtain a dispersion of solid dye fine particles having an average particle diameter of 0.2 μm.

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<Preparation of Support> In preparing the light-sensitive material, the support, undercoat layer, antistatic layer (back first layer), magnetic recording layer (back second layer), and back third layer were formed as follows. It was formed as follows.

(1) Preparation of Support Polyethylene-2,6-naphthalenedicarboxylate (PEN)
After 100 parts by weight and 2 parts by weight of Tinuvin P.326 (manufactured by Ciba-Geigy) as an ultraviolet absorber were uniformly mixed, the mixture was melted at 300 ° C. and extruded from a T-die. The extruded product was subjected to a longitudinal stretching of 3.3 times at 140 ° C., followed by a transverse stretching of 4.0 times, and further heat-set at 250 ° C. for 6 seconds to obtain a thickness of 9 mm.
A 0 μm PEN film was obtained. The PEN film has a blue dye, a magenta dye, and a yellow dye (public technical report: I-1, I-4, I-6, I-24, and
I-26, I-27, II-5) were added in appropriate amounts. In addition, the diameter 30
The sheet was wound around a stainless steel core having a length of 110 cm and a heat history of 48 hours was given at 110 ° C., so that a support having little curl was formed.

(2) Application of Undercoat Layer Both sides of the PEN support were subjected to glow treatment in the following manner.
Four rod-shaped electrodes having a diameter of 2 cm and a length of 40 cm were fixed on an insulating plate in a vacuum tank at intervals of 10 cm. At this time, it was set so that the film traveled 15 cm away from the electrode. A heating roll with a temperature controller with a diameter of 50 cm was installed just before the electrode, and the film was
It was set to make four round contacts. 90μm thick, 30cm wide 2
The axially stretched film was run and heated with a heating roll such that the temperature of the film surface between the heating roll and the electrode zone was 115 ° C. Then, the film was conveyed at a speed of 15 cm / sec to a vacuum chamber for glow treatment.

The glow treatment was performed by setting the pressure in the vacuum chamber to 26.5 Pa and the partial pressure of H ₂ O in the atmospheric gas to 75%. The discharge frequency was 30 KHz, the output was 2500 W, and the treatment intensity was 0.5 kV · A · min / m ² . The procedure of the vacuum glow discharge treatment was as described in JP-A-7-3056.

An undercoat layer was provided on one side (emulsion side) of the glow-treated PEN support according to the following formulation. 0.02μ dry film thickness
Designed to be m. Drying conditions were 115 ° C. for 3 minutes.

Gelatin 83 parts by weight Water 291 parts by weight Salicylic acid 18 parts by weight Aerosil R972 1 part by weight (Colloidal silica manufactured by Nippon Aerosil Co., Ltd.) Methanol 6900 parts by weight n-propanol 830 parts by weight Polyamide-epichlorohydrin resin 25 parts by weight (Described in JP-A-51-3619)

(3) Coating of antistatic layer (back first layer) 40 parts by weight of SN-100 (conductive fine particles manufactured by Ishihara Sangyo Co., Ltd.) and water
After roughly dispersing with a stirrer while adding a 1N aqueous solution of sodium hydroxide to 60 parts by weight of the mixture, the mixture is dispersed with a horizontal sand mill, and the secondary particles have an average particle diameter of 0.06 μm. I got

On a PEN support (back side) having a surface treated with a coating solution having the following composition, the coating amount of the conductive fine particles was 270 mg.
/ m ² . Drying conditions were 115 ° C. and 3 minutes.

SN-100 (conductive fine particles, manufactured by Ishihara Sangyo Co., Ltd.) 270 parts by weight Gelatin 23 parts by weight Rheodol TW-L120 (surfactant, manufactured by Kao Corporation) 6 parts by weight Denacol EX-521 (Nagase Chemical Co., Ltd.) Industrial Co., Ltd., hardener) 9 parts by weight Water 5000 parts by weight

(4) Coating of magnetic recording layer (back second layer) Magnetic particles CSF-4085V2 (manufactured by Toda Kogyo Co., Ltd.
-Fe ₂ O ₃ ) on the surface, 16% by weight of magnetic particles X-12-6
41 (a silane coupling agent manufactured by Shin-Etsu Chemical Co., Ltd.) was subjected to a surface treatment.

A coating solution having the following composition was applied on the back first layer.
The amount of CSF-4085V2 treated with silane coupling agent is 62
The composition was applied so as to be mg / m ² . The dispersion method of the magnetic particles and the abrasive was in accordance with the method described in JP-A-6-35092. Drying conditions were 115 ° C. and 1 minute.

Diacetylcellulose (binder) 1140 parts by weight X-12-641 treated CSF-4085V2 (magnetic particles) 62 parts by weight AKP-50 (alumina manufactured by Sumitomo Chemical Co., Ltd., abrasive) 40 parts by weight Millionate MR-400 ( Nippon Polyurethane Co., Ltd., hardener) 71 parts by weight Cyclohexanone 12000 parts by weight Methyl ethyl ketone 12000 parts by weight

The X-light (blue filter) increases the DB color density of the magnetic recording layer by about 0.1, the saturation magnetization moment of the magnetic recording layer is 4.2 emu / g, the coercive force is 7.3 × 10 ⁴ A / m,
The squareness ratio was 65%.

(5) Coating of Back Third Layer A third back layer was coated on the magnetic recording layer side of the photosensitive material. Wax (1-2) having the following structure is emulsified and dispersed in water using a high-pressure homogenizer, and has a concentration of 10% by weight and a weight average diameter of 0.25 μm.
A wax aqueous dispersion was obtained. Wax (1-2) nC ₁₇ H ₃₅ COOC ₄₀ H ₈₁ -n

A coating solution having the following composition was applied onto the magnetic recording layer (back second layer) so that the amount of wax applied was 27 mg / m ² . Drying conditions were 115 ° C. and 1 minute.

The above wax aqueous dispersion (10% by weight) 270 parts by weight Pure water 176 parts by weight Ethanol 7123 parts by weight Cyclohexanone 841 parts by weight

Further, an emulsified dispersion containing a coupler and a built-in developing agent was prepared. Yellow coupler (CP-107) 8.
95 g, compound (DEVP-23) 3.65 g, antifoggant (d) 0.17
g, (e) 0.28 g, high boiling point organic solvent (g) 9.08 g and ethyl acetate 50.0 ml were mixed at 60 ° C. The obtained solution was mixed with 200 g of an aqueous solution in which 18.0 g of lime-processed gelatin and 0.8 g of sodium dodecylbenzenesulfonate were dissolved, and emulsified and dispersed at 10,000 rpm for 20 minutes using a dissolver stirrer. Then add distilled water to make the total volume 300 g, and add 200 g
Mix at 0 rpm for 10 minutes.

A yellow coupler dispersion in which the compound (DEVP-23) was changed to 10.75 g of DEVP-26, and the compound (DEVP-23) was replaced with 10.75 g of DEVP-26
A yellow coupler dispersion changed to 75 g of DEVP-50 was also prepared.

[0278]

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[0279]

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Similarly, a dispersion of a magenta coupler and a cyan coupler was prepared. Magenta coupler (CP-205) 4.68
g, (CP-210) 2.38 g, compound (DEVP-23) 2.76 g, antifoggant (d) 0.11 g, high boiling organic solvent (g) 7.52 g, and ethyl acetate 38.0 ml were mixed at 60 ° C. The obtained solution was mixed with 150 g of an aqueous solution in which 12.2 g of lime-processed gelatin and 0.8 g of sodium dodecylbenzenesulfonate were dissolved, and emulsified and dispersed at 10,000 rpm for 20 minutes using a dissolver stirrer. Thereafter, distilled water was added so that the total amount became 300 g, and the mixture was mixed at 2,000 rpm for 10 minutes.

A magenta coupler dispersion in which the compound (DEVP-23) was changed to 8.13 g of DEVP-26, and the compound (DEVP-23) was converted to 8.1
A magenta coupler dispersion changed to 3 g of DEVP-50 was also prepared.

Cyan coupler (CP-324) 7.32 g, cyan coupler (CP-320) 3.10 g, developing agent (DEVP-23) 4.36 g, antifoggant (d) 0.15 g, high boiling organic solvent (g) 11.62 g,
And 38.0 ml of ethyl acetate were mixed at 60 ° C. The obtained solution was mixed with 150 g of an aqueous solution in which 12.2 g of lime-processed gelatin and 0.8 g of sodium dodecylbenzenesulfonate were dissolved, and emulsified and dispersed at 10,000 rpm for 20 minutes using a dissolver stirrer. Thereafter, distilled water was added so that the total amount became 300 g, and the mixture was mixed at 2,000 rpm for 10 minutes.

A cyan coupler dispersion in which the compound (DEVP-23) was changed to 12.85 g of DEVP-26, and the compound (DEVP-23) was changed to 12.85 g
A cyan coupler dispersion was also prepared in which g was changed to DEVP-50.

Further, a dispersion of a dye for coloring the intermediate layer as a filter layer and an antihalation layer was prepared in the same manner. The dyes and the high-boiling organic solvents used to disperse them are shown below.

[0285]

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[0286]

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Further, as a filter layer and an antihalation layer, a dispersion of a dye which was reversibly erased upon heating for coloring the intermediate layer was prepared.

<Preparation of Dye Dispersion for Yellow Filter (YH) Layer> 10 g of leuco dye (1), 40 g of stearyl alcohol and 10 g of developer (SD-1) were dissolved in 200 ml of ethyl acetate. The resulting solution was mixed with 600 g of an aqueous solution in which 2.0 g of surfactant (r) was dissolved, and 100
It was emulsified and dispersed at 00 rpm for 20 minutes. Thereafter, the mixture was stirred at 50 ° C. for 30 minutes under a nitrogen stream to remove ethyl acetate, added with 30 g of lime-processed gelatin, added with distilled water so that the total amount became 750 g, and mixed at 2,000 rpm for 10 minutes.

The leuco dye (1) was replaced with a leuco dye (2) and a leuco dye (3), respectively, and a magenta filter (MF) was used.
Dye dispersions, antihalation (AH) dye dispersions were similarly prepared.

[0290]

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[0291]

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Using these emulsions, photosensitive material samples 101, 102 and 103 for multilayer color thermal development shown in Table 1 were prepared.

(Unit is parts by mass)

[Table 1]

[0294]

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<Preparation of SCC-10 dispersion> 9.95 g of SCC-10,
7.08 g of high boiling organic solvent (f) and 25.0 ml of ethyl acetate were mixed at 60 ° C. The resulting solution was treated with 18.0 g of lime-processed gelatin and sodium dodecylbenzenesulfonate.
8 g was dissolved in 200 g of an aqueous solution, and emulsified and dispersed at 10,000 rpm for 20 minutes using a dissolver stirrer. Thereafter, distilled water was added so that the total amount became 300 g, and the mixture was mixed at 2,000 rpm for 10 minutes.

[0296]

Embedded image A similar photosensitive material 201 was prepared except that the SCC-10 dispersion prepared as described above was added to the yellow filter layer and the magenta filter layer of the photosensitive material 101. SCC-10 was equimolar to the developing agent.

<Preparation of SCC-32 dispersion> 9.95 g of SCC-32,
7.08 g of high boiling organic solvent (j) and 25.0 ml of ethyl acetate were mixed at 60 ° C. The resulting solution is lime-processed gelatin
18.0 g and sodium dodecylbenzenesulfonate 0.8
g was dissolved in 200 g of an aqueous solution, and emulsified and dispersed at 10,000 rpm for 20 minutes using a dissolver stirrer. After that, add distilled water so that the total amount becomes 300 g.
Mix for 0 minutes.

[0298]

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The SCC-32 prepared as described above was added to the yellow filter layer and the magenta filter layer of the photosensitive materials 102 and 103.
Light-sensitive materials 202 and 203 were prepared in the same manner except that the dispersion was added. SCC-32 was equimolar to the developing agent.

These photosensitive material samples 101 to 103 and 201 to 203
Method of cutting out a sample from the sample and determining the ISO sensitivity (ANSI PH
2.27), with a white light source at 500 lux through a continuous optical wedge
A / 100 second exposure was applied. Using a heat drum after exposure, samples 101 and 201 were thermally developed at 110 ° C. for 20 seconds, and samples 102 and 202 were developed.
Samples 103 and 203 were thermally developed at 150 ° C. for 20 seconds.

The transmission density of the sample developed by heat development was measured to determine fog and ISO sensitivity. Photosensitive material sample 1
Separately, two pieces of each of samples 01 to 103 and 201 to 203 were prepared, and instead of the above white light exposure, red light exposure (exposure through Fuji filter SC62) and green light exposure (through Fuji filter BPN53) Exposure).
These exposed samples were thermally developed in the same manner as described above, and the transmission densities were measured in the same manner as described above. The following values were read from the HD curves thus obtained and used as indices of color mixing.

Gr: G density at the exposure amount when R density gives Dmin + 1.0 in red exposure. It is an indicator of color mixing from the red photosensitive layer to the green photosensitive layer. Bg: B density at the exposure amount when G density gives Dmin + 1.0 in green exposure. It serves as an indicator of color mixing from the green photosensitive layer to the blue photosensitive layer. Table 2 shows the fog, sensitivity, Gr and Bg values thus obtained.

[0303]

[Table 2]

From the results shown in Table 2, it is clear that the samples 201 to 203 using the compounds of SC-1 and SC-2 of the present invention have little fog and color mixture.

The photosensitive material samples 101 to 103 and 201 to 203 were cut into a 135 negative film size, perforated, loaded into a camera, and photographed with a person and a Macbeth chart. The image on the processed photosensitive material is read by a digital image reading device (Frontier SP-1000, manufactured by Fuji Photo Film Co., Ltd.), processed on a workstation, and processed with a heat developing printer ( PICTROGRAPHY3000, manufactured by Fuji Photo Film Co., Ltd.)

The samples 103 and 203 were read at the time of reading by feeding warm air to the surface of the photosensitive material with a drier so that the film surface temperature would be 60 ° C. to 70 ° C. Processed photosensitive material 101
In prints obtained from ~ 103, only images with low saturation can be obtained due to color mixing, and color correction processing to increase saturation while maintaining color reproduction by digital signal processing using the Macbeth chart in the image. In this case, the color conversion correction coefficient becomes large, so that reading noise and image unevenness are emphasized, and good image quality cannot be obtained. On the other hand, processed photosensitive material
In the images obtained from 201 to 203, color turbidity due to inter-layer color mixture is reduced, a high-saturation print is obtained, and even if the same color correction processing is performed, the color conversion correction coefficient is small, so the image quality is slightly degraded. Met.

Comparative Example 1 The SCC-10 dispersion or the dispersion was added to the intermediate layer of the light-sensitive materials 201 to 203 of the present invention.
A photosensitive composition having the same structure as in Example 1 except that a dispersion of 2,5-dioctylhydroquinone prepared in the same manner as above was added so that the number of moles was equal to that of SCC-10, instead of adding the SCC-32 dispersion. Materials 301 to 303 were created.

Table 3 shows the fog when the photosensitive materials 301 to 303 were similarly exposed and heat-developed and the fog when exposed and heat-developed after being stored in an environment of 60 ° C. and 60% humidity for one week.

[0309]

[Table 3]

As is clear from the comparison between Tables 2 and 3,
When known hydroquinones were added to the intermediate layer, the processing fog at the time of thermal development processing was large, and the photographic property fluctuation (fog) at the time of storage of the unexposed photosensitive material was large.

Example 2 Using the same silver halide emulsion as in Example 1, different photosensitive materials 401 to 403 such as couplers, developing agents, organic silver salts and mercapto compounds were prepared by the following method. An emulsified dispersion containing the coupler was prepared as follows.

8.95 g of yellow coupler (CP-115), 0.90 g of development accelerator (X), 4.54 g of high boiling organic solvent (z), 4.54 g of high boiling organic solvent (h) and 50.0 ml of ethyl acetate were added at 60 ° C. Mixed. The obtained solution was mixed with 200 g of an aqueous solution in which 18.0 g of lime-processed gelatin and 0.8 g of sodium dodecylbenzenesulfonate were dissolved, and mixed using a dissolver stirrer.
Emulsified and dispersed at 0000 rpm for 20 minutes. Then the total amount is 30
Distilled water was added so as to obtain 0 g, and the mixture was mixed at 2,000 rpm for 10 minutes.

An emulsion was similarly prepared by changing 8.95 g of the yellow coupler (CP-115) to 8.95 g of the yellow coupler (CP107).

[0314]

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Similarly, a dispersion of a magenta coupler and a cyan coupler was prepared. Magenta coupler (CP-217) 4.68
g, (CP-210) 2.38 g, development accelerator (X) 0.71 g, high boiling organic solvent (z) 7.52 g and ethyl acetate 38.0 ml were mixed at 60 ° C. The resulting solution was mixed with 150 g of an aqueous solution in which 12.2 g of lime-processed gelatin and 0.8 g of sodium dodecylbenzenesulfonate were dissolved, and mixed using a dissolver stirrer.
Emulsified and dispersed at 0000 rpm for 20 minutes. Then the total amount is 30
Distilled water was added so as to obtain 0 g, and the mixture was mixed at 2,000 rpm for 10 minutes.

Further, 4.68 g of a magenta coupler (CP-217),
(CP-210) 2.38 g, magenta coupler (CP-20
5) Emulsions were prepared in the same manner by changing to 4.68 g and 2.38 g of (CP-210).

[0317] 7.32 g of cyan coupler (CP-325), 3.10 g of cyan coupler (CP-311), 1.04 g of development accelerator (X), 11.62 g of high boiling organic solvent (z) and 38.0 ml of ethyl acetate were added at 60 ° C. Mixed. The obtained solution was mixed with 150 g of an aqueous solution in which 12.2 g of lime-processed gelatin and 0.8 g of sodium dodecylbenzenesulfonate were dissolved, and emulsified and dispersed at 10,000 rpm for 20 minutes using a dissolver stirrer. Thereafter, distilled water was added so that the total amount became 300 g, and the mixture was mixed at 2,000 rpm for 10 minutes.

Further, 7.32 g of the cyan coupler (CP-325) and 3.10 g of the cyan coupler (CP-311) were each added to the cyan coupler.
An emulsion was prepared in the same manner except that 7.32 g of (CP-324) and 3.10 g of cyan coupler (CP-320) were used.

(Preparation of solid dispersion of active substance) Built-in developing agent DE
The microcrystal dispersion of VP-56 was prepared by the following method. To 50 g of the built-in developing agent DEVP-56 and 30 g of a 10% by mass aqueous solution of a modified polyvinyl alcohol (Poval MP203 manufactured by Kuraray Co., Ltd.), 0.5 gg of alkanol XC and 100 g of water were added and mixed well.
A slurry was obtained. The slurry was fed by a diaphragm pump, and was fed to a horizontal sand mill (UVM-2: manufactured by Imex Co., Ltd.) filled with zirconia beads having an average diameter of 0.5 mm.
After time dispersion, water was added to adjust the concentration of the target compound to 10% by mass to obtain a dispersion of the target compound. The particles contained in the dispersion of the target compound thus obtained had a median diameter of 0.30 μm and a maximum particle diameter of 1.0 μm or less. The resulting dispersion of the target compound was filtered through a polypropylene filter having a pore size of 10.0 μm to remove foreign substances such as dust. Immediately before use, the mixture was again filtered through a polypropylene filter having a pore size of 10 μm.

The microcrystal dispersion of the internal developing agent DEVP-60 was
Created by the following method. Built-in developing agent DEVP-60 50 g and modified polyvinyl alcohol (Poval MP20 manufactured by Kuraray Co., Ltd.)
3) 30 g of 10% by mass aqueous solution was added to Surf Chemicals Surf
1.0 g of actant10G and 100 g of water were added and mixed well to obtain a slurry. The slurry was sent by a diaphragm pump and dispersed in a horizontal sand mill (UVM-2: manufactured by Imex Co., Ltd.) filled with zirconia beads having an average diameter of 0.5 mm for 6 hours, and water was added to reduce the concentration of the target compound. It was adjusted to 10% by mass to obtain a dispersion of the target compound. The particles contained in the dispersion of the target compound thus obtained had a median diameter of 0.50 μm and a maximum particle diameter of 1.5 μm or less. The resulting dispersion of the target compound was filtered with a polypropylene filter having a pore size of 10.0 μm to remove foreign substances such as dust.
Immediately before use, the mixture was again filtered with a polypropylene filter having a pore size of 10 μm.

(Preparation method of silver salt of 1-phenyl-5-mercaptotetrazole) 431 g of lime-treated gelatin and 6
569 ml of distilled water was charged. Next, a solution B was prepared by mixing 320 g of 1-phenyl-5-mercaptotetrazole with 2044 ml of distilled water and 790 g of a 2.5 M aqueous sodium hydroxide solution. Solution B and, if necessary, nitric acid or sodium hydroxide were added to the mixture in the reaction vessel to adjust pAg to 7.25 and pH 8.00.
Under strong stirring, 3200 ml of an aqueous solution of 0.54 M silver nitrate was added to the above reaction vessel at a rate of 250 ml / min.At the same time, while controlling the pAg of the reaction solution at 7.25, the solution B was added to the solution near the stirrer. Was added. After completion of the addition, the mixture was concentrated by ultrafiltration to obtain a dispersion containing fine particles of silver salt of 1-phenyl-5-mercaptotetrazole.

<Method for Preparing Silver Benzotriazole> 0.34 g of benzotriazole, 0.24 g of sodium hydroxide and 25 g of phthalated gelatin were dissolved in 700 ml of water, kept at 60 ° C., and stirred. Next, a solution of 3.4 g of benzotriazole and 1.2 g of sodium hydroxide dissolved in 150 ml of water, and 5 g of silver nitrate in water
The solution dissolved in 150 ml was simultaneously added to the above solution over 4 minutes. After stirring for 5 minutes, a solution of 3.4 g of benzotriazole and 1.2 g of sodium hydroxide in 150 ml of water and a solution of 5 g of silver nitrate in 150 ml of water were simultaneously added to the above solution in the vicinity of the stirrer in 6 minutes. The emulsion was allowed to settle by adjusting the pH of the emulsion to remove excess salt.
Thereafter, the pH was adjusted to 6.0 to obtain a silver benzotriazole emulsion having a yield of 470 g.

Using the above coupler emulsion, microcrystal dispersion of a built-in developing agent, and silver 1-phenyl-5-mercaptotetrazole, color photographic material samples 401 and 4 having a multilayer structure shown in Table 4
02 was created.

(Unit is parts by mass)

[Table 4]

The prepared samples 401 and 402 were processed in the same manner as in Example 1, mounted on a camera, and photographed a person and a Macbeth chart at ISO 400 setting. Photo-sensitive material samples 401 and 402
Was heated at 155 ° C. for 15 seconds, the obtained image was digitally read, and printed after image processing. As a result, a print with high saturation was obtained as in Example 1.

A microcrystal dispersion of the built-in developing agent of the photosensitivity material sample 401 was replaced with the microcrystal dispersion of DEVP-56 by an equal weight, and a photosensitivity material sample 403 was prepared in the same manner as the photosensitivity material sample 401 except for the rest. did.

The prepared photosensitive material sample 403 was processed in the same manner as the sample 401, loaded into a camera, and photographed a person and a Macbeth chart at ISO 200 setting. Photographed photosensitive material sample 403 at 160 ° C
After heating for 15 seconds, the obtained image was digitally read and printed after image processing. As a result, a print with high saturation was obtained as in Sample 401.

Example 3 According to the method described in the example of US Pat. No. 5,840,475,
A silver halide emulsion composed of high silver chloride tabular grains was prepared.

To a silver iodochloride (100) tabular emulsion reaction vessel were added 1.48 g of sodium chloride, 0.28 g of potassium iodide, 38.8 g of oxidized lime-processed gelatin and distilled water to make 4.5 L, and the temperature was adjusted to 35 ° C. Kept. In this solution,
Under vigorous stirring, a 4 M aqueous solution of silver nitrate containing 0.32 g / L of mercuric chloride (hereinafter referred to as solution 1) and a 4 M aqueous solution of sodium chloride were added at an addition rate of 21 ml / min for 30 seconds. Was formed. Immediately thereafter, 0.39 g / L sodium chloride and 0.12 g
Add 9.1 L of an aqueous solution containing g / L of potassium iodide and add
Hold for a minute. Subsequently, the above solution 1 was added under the conditions shown in the following table to form silver halide grains. At this time, a 4 M aqueous sodium chloride solution was simultaneously controlled and added so that the pCl of the reaction solution was 2.2.

At the end of the particle growth stage II, a 4 M aqueous sodium chloride solution was added at an addition rate of 14 ml / min for 5 minutes and kept for 30 minutes. Thereafter, solution 1 was added at an addition rate of 14 ml / min for 5 minutes, followed by 70% containing 5.25 g of potassium iodide.
After adding 20 ml of the aqueous solution and keeping it for 20 minutes, the solution 1 was added to 14 ml /
The mixture was added at a rate of 1 minute for 8 minutes, and a 4 M aqueous sodium chloride solution was simultaneously controlled so that the pCl of the system became 2.2. At this time, potassium hexacyanoruthenate is contained in the aqueous sodium chloride solution at a concentration of 3 × with respect to all silver halide.
It was contained to a concentration of 10 ^-5 molar. After the completion of particle formation, sedimentation, washing with water, and desalting were performed according to a conventional method.

The emulsion thus obtained is tabular grains having an average diameter of 0.56 μm in terms of the diameter of a circle equivalent to the projected area, an average thickness of the grains of 0.09 μm, and the (100) plane is defined as the main plane. Tabular grains were contained at a ratio of 70% or more of the total projected area of the silver halide grains. This emulsion was designated as emulsion u.

In the method for preparing the emulsion u, by adjusting the temperature and time for forming grains under different conditions, the average grain size at the diameter of a circle equivalent to the projected area is 1.60 μm and the mean thickness of the grains is 0.114 μm. An emulsifier was prepared which contained tabular grains having a (100) plane as a main plane at a ratio of 70% or more of the total projected area of the silver halide grains. This emulsion was designated as emulsion m.

In the method for preparing the emulsion u, by adjusting the temperature and time for forming grains under different conditions, the average grain size at a circle diameter equivalent to the projected area is 2.90 μm and the average grain thickness is 0.121 μm. An emulsifier was prepared which contained tabular grains having a (100) plane as a main plane at a ratio of 70% or more of the total projected area of the silver halide grains.
This emulsion was designated as emulsion o.

These emulsions were subjected to chemical sensitization and spectral sensitization in the same manner as in Example 1 to prepare blue-, green-, and red-sensitive emulsions. Blue-sensitized emulsions ob, mb, ub, and green sensitized emulsions were prepared. Emulsion og, mg, u
-g, red sensitized emulsion or, mr, ur.

Emulsions A-1b and A of photosensitive material sample 401 of Example 2
-2b, A-3b, A-1g, A-2g, A-3g, A-1r, A-2r, A-3r, respectively, blue sensitized emulsion ob, mb, ub, green sensitized emulsion og, m -
Photosensitive material 5 changed to g, ug, red sensitized emulsion or, mr, ur
01 was created. The emulsions of the light-sensitive material samples 402 and 403 of Example 2 were similarly changed, and light-sensitive material samples 502 and 503 were prepared in the same manner.

These photosensitive materials also exhibited good photographic characteristics. When samples 501 to 503 were subjected to exposure and heat development in the same manner as in Example 1, prints with little color turbidity and high chroma were obtained. .

To a silver (111) iodochloride (111) emulsion reaction vessel, 9.3 g of sodium chloride, 2.84 g of 7-azaindole and 80 g of lime-processed bone gelatin and distilled water were added to make 3.9 L and kept at 50 ° C. . After adjusting the pH of the solution to 5.5, 2 M silver nitrate aqueous solution was added to this solution with vigorous stirring.
Nuclei were formed by addition at a rate of ml / min for 36 seconds. Immediately thereafter, an aqueous silver nitrate solution was added under the conditions shown in the following table to form silver halide grains. At this time, the pCl of the reaction solution was 1.5
4 M aqueous sodium chloride solution was added at the same time so that Particle growth stage Silver nitrate solution Initial flow rate Final flow addition time I 2 M 8 ml / min 16 ml / min 2.8 min II 4 M 8 ml / min 30 ml / min 15 min III 4 M 30 ml / min 30 ml / min 4 min

One minute after the completion of the grain growth step, a 4 M silver nitrate aqueous solution was added at a rate of 23 ml / min for 2.4 minutes.
The pCl of the system is 3.6
M and an aqueous solution of 0.4 M as potassium iodide were simultaneously added while being controlled. At this time, potassium hexacyanoruthenate was contained in the aqueous sodium chloride / potassium iodide solution at a concentration of 3 × 10 ⁻⁵ M with respect to all silver halides. After the completion of particle formation, sedimentation, washing with water, and desalting were performed according to a conventional method.

The emulsion thus obtained had an average grain size of 0.86 μm at a circle diameter equivalent to the projected area and an average grain thickness of 0.10 μm.
Tabular grains having the (111) plane as the main plane were contained at a ratio of 70% or more of the total projected area of the silver halide grains.
This emulsion was designated as emulsion u '.

In the method for preparing the emulsion u ', by adjusting the temperature and time for grain formation to different conditions, the average grain size at the diameter of the circle equivalent to the projected area is 1.58 μm, and the average grain thickness is 0.119 μm. An emulsion was prepared which contained the tabular grains having the (111) plane as the main plane at a ratio of 70% or more of the total projected area of the silver halide grains. This emulsion was designated as emulsion m '.

In the method for preparing the emulsion u ', the temperature and time for forming the grains were adjusted so that the average grain size at the diameter of the circle equivalent to the projected area was 2.85 μm and the average thickness of the grains was 0.131 μm. An emulsion was prepared which contained tabular grains, each having a (111) plane as a main plane, in a proportion of 70% or more of the total projected area of the silver halide grains. Emulsion o '
And

These emulsions were subjected to chemical sensitization and spectral sensitization in the same manner as in Example 1 to prepare blue-, green-, and red-sensitive emulsions. Blue-sensitized emulsions o'-b and m'-b , U'-b, green sensitized emulsion o'-g, m '
-g, u'-g, and red sensitized emulsions o'-r, m'-r, u'-r were obtained.

Emulsions A-1b and A of photosensitive material sample 401 of Example 2
-2b, A-3b, A-1g, A-2g, A-3g, A-1r, A-2r, A-3r, respectively, blue-sensitized emulsions o'-b, m'-b, u ' -b Green sensitized emulsion o'-
g, m'-g, u'-g, and red sensitized emulsions o'-r, m'-r, and u'-r were used to prepare a light-sensitive material 601. Photosensitive material sample 4 of Example 2
Photosensitive materials in which emulsions of 02 and 403 were similarly changed, samples 602 and 60
3 was created similarly.

These photosensitive materials also exhibited good photographic characteristics. When samples 601 to 603 were subjected to exposure and heat development in the same manner as in Example 1, prints with little color turbidity and high chroma were obtained. .

[0345]

As described in detail above, the light-sensitive material of the present invention is a color image of high color saturation with little color mixing without increasing fog and deteriorating raw storage properties, especially in a heat development system. Is extremely useful as a silver halide color photographic light-sensitive material.

[Brief description of the drawings]

FIG. 1 is a longitudinal sectional view showing an example of a heat developing machine used for a heat development process of a photothermographic material of the present invention.

[Explanation of symbols]

 10: Thermal developing photosensitive material 11: Loading roller pair 12: Loading roller pair 13: Roller 14: Smooth surface 15: Heater 16: Guide plate

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) G03C 5/08 351 G03C 5/08 351

Claims (9)

[Claims] 1. The method according to claim 1, wherein at least (a)
Photosensitive silver halide, (b) a reducible silver salt, (c)
(I) a color developing agent represented by (D), a coupler that reacts with the color developing agent to form a dye, (e) the following general formula (SC-1)
Or at least one of the compounds represented by the following general formula (SC-2)
A photothermographic material comprising: a seed; and (f) a binder. Embedded image (In the general formula (I), R ₁ , R ₂ , R ₃ and R ₄ each independently represent a hydrogen atom or a substituent, and R ₅ and R ₆ each independently represent a substituted or unsubstituted alkyl group, aryl Represents a group, a heterocyclic group, an acyl group, an alkylsulfonyl group, or an arylsulfonyl group, R ₁ and R ₂ , R ₃ and R ₄ , R ₅ and R ₆ , R ₂ and
R ₅ and / or R ₄ and R ₆ may combine with each other to form a 5-, 6- or 7-membered ring. R ₇ is R ₁₁ -O-CO-, R ₁₂ -CO-CO
-, R ₁₃ -NH-CO-, R ₁₄ -SO _2- , R ₁₅ -WC (R ₁₆ ) (R ₁₇ )-[W represents an oxygen atom, a sulfur atom or> NR ₁₈ ], R ₁₉ -SO ₂ -NH-
CO- or (M ₁ ) _{1 / n} OSO _2- , R ₁₁ , R ₁₂ , R ₁₃ , R ₁₄ and R
₁₉ represents a substituted or unsubstituted alkyl group, an aryl group, or a heterocyclic group, R ₁₅ represents a hydrogen atom or a block group, R ₁₆ , R ₁₇ and R ₁₈ are a hydrogen atom, or a substituted or unsubstituted alkyl And M ₁ represents an n-valent cation. ) (In the general formula (SC-1), R ₂₁ represents a hydrogen atom or a substituent, and R ₂₂ represents a substituted or unsubstituted alkyl group, alkenyl group, alkynyl group, aryl group, heterocyclic group, alkoxycarbonyl group, aryl R ₂₃ represents a hydrogen atom or a substituted or unsubstituted alkyl group, alkenyl group, alkynyl group, aryl group or heterocyclic group, and in general formula (SC-2),
₂₄ represents a substituted or unsubstituted alkyl group, alkenyl group, alkynyl group, aryl group, heterocyclic group, alkoxy group, aryloxy group, heterocyclic oxy group, amino group or anilino group, and R ₂₅ is substituted or unsubstituted And R ₂₆ represents a substituted or unsubstituted alkyl group, alkenyl group, alkynyl group, aryl group or heterocyclic group. R ₂₄ and R ₂₆ may combine to form a 5- to 7-membered ring. ) 2. The photothermographic material according to claim 1, wherein R _{7 of the} color developing agent represented by the general formula (I) is represented by the following formula (T-1). Photothermographic material. BLK-W- (X = Y) _j -C (R ₃₁ ) (R ₃₂ ) -O-CO- (T-1) (In the formula (T-1), BLK represents a block group, and W Represents an oxygen atom, a sulfur atom or> NR ₃₃ ; X and Y each represent a substituted or unsubstituted methine or nitrogen atom;
Or R 2, and R ₃₁ , R ₃₂ and R ₃₃ each represent a hydrogen atom or a substituent. ) 3. The photothermographic material according to claim 1, wherein the base or the nucleophile is heated by heat on the same surface as the surface containing the components (a) to (f) with respect to the support. A photothermographic material comprising a compound that releases an agent. 4. The photothermographic material according to claim 1, wherein the reducible silver salt is a compound having a triazole group. 5. The photothermographic material according to claim 1, further comprising at least three kinds of silver halide photosensitive layers having different spectral sensitivities, wherein the non-photosensitive layer between the photosensitive layers has the general structure. A photothermographic material for color photography, comprising at least one compound selected from formula (SC-1) and formula (SC-2). 6. The photothermographic material according to claim 1, further comprising a silver halide emulsion layer containing 50% or more of silver halide tabular grains having an aspect ratio of 8 to 50. Characteristic photothermographic material. 7. The photothermographic material according to claim 1, further comprising a compound represented by the following general formula (F-1) or (F-2). Developed photosensitive material. Embedded image (In the general formula (F-1), R _f1 represents an alkyl group having 4 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or an aralkyl group having 7 to 20 carbon atoms, and M ₂ represents a hydrogen atom or a cation. Represents the following.) (In the general formula (F-2), R _f2 is a hydrogen atom, and has 4 to 20 carbon atoms.
Represents an alkyl group, an aryl group having 6 to 20 carbon atoms, or an aralkyl group having 7 to 20 carbon atoms, and R _f3 represents an alkyl group having 4 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or a carbon atom having 7 carbon atoms. ~
An aralkyl group of 20, M ₂ represents a hydrogen atom or a cation. However, the total number of carbon atoms of R _f2 and R _f3 is 4 to 30. ) 8. The photothermographic material according to claim 7, wherein the compound represented by the general formula (F-1) or (F-2) is a poorly water-soluble metal salt. Photothermographic material. 9. A color image is formed by exposing the photothermographic material according to claim 1 to imagewise exposure and heating the photothermographic material at a temperature of 60 ° C. to 180 ° C. for 5 seconds to 60 seconds. An image forming method comprising: photoelectrically reading image information formed on the photosensitive material; and forming an image on another recording material based on the image information.